CN109415474A - Silicone hydrogels comprising high-content polyamide - Google Patents

Silicone hydrogels comprising high-content polyamide Download PDF

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Publication number
CN109415474A
CN109415474A CN201780042041.9A CN201780042041A CN109415474A CN 109415474 A CN109415474 A CN 109415474A CN 201780042041 A CN201780042041 A CN 201780042041A CN 109415474 A CN109415474 A CN 109415474A
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methyl
hydroxyl
silicone hydrogels
poly
group
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CN109415474B (en
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A.阿里
A.古兹曼
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Johnson and Johnson Vision Care Inc
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Johnson and Johnson Vision Care Inc
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
    • C08F283/122—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes on to saturated polysiloxanes containing hydrolysable groups, e.g. alkoxy-, thio-, hydroxy-
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D11/00—Producing optical elements, e.g. lenses or prisms
    • B29D11/00009—Production of simple or compound lenses
    • B29D11/00038—Production of contact lenses
    • B29D11/00125—Auxiliary operations, e.g. removing oxygen from the mould, conveying moulds from a storage to the production line in an inert atmosphere
    • B29D11/00134—Curing of the contact lens material
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    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
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    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
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    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
    • C08J3/075—Macromolecular gels
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    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3472—Five-membered rings
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    • C08L101/00—Compositions of unspecified macromolecular compounds
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    • C08L39/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Compositions of derivatives of such polymers
    • C08L39/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
    • C08L39/06—Homopolymers or copolymers of N-vinyl-pyrrolidones
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    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/08—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
    • C08L51/085—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds on to polysiloxanes
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    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
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    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • G02B1/041—Lenses
    • G02B1/043—Contact lenses
    • G—PHYSICS
    • G02—OPTICS
    • G02C—SPECTACLES; SUNGLASSES OR GOGGLES INSOFAR AS THEY HAVE THE SAME FEATURES AS SPECTACLES; CONTACT LENSES
    • G02C7/00—Optical parts
    • G02C7/02—Lenses; Lens systems ; Methods of designing lenses
    • G02C7/04—Contact lenses for the eyes
    • G02C7/049—Contact lenses having special fitting or structural features achieved by special materials or material structures
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    • C08G2210/00—Compositions for preparing hydrogels
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    • C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
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    • C08J2477/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
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    • C08L2203/00—Applications
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    • C08L39/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Compositions of derivatives of such polymers

Abstract

The present invention describes the silicone hydrogels with high-content polyamide, shows the balance of excellent physics, machinery and biological nature.Silicone hydrogels are formed by reactive monomer mixture, and the reactive monomer mixture includes: (methyl) acrylic acid hydroxy alkyl ester monomer；Hydroxyl organosilicon composition；And polyamide, wherein the total weight based on reactive component in reactive monomer mixture, the polyamide exists with the amount greater than 15 weight %.

Description

Silicone hydrogels comprising high-content polyamide
Related application
U.S. Patent application 15/609,079 and 2016 year July 6 that patent application claims were submitted on May 31st, 2017 The priority for the U.S. Provisional Patent Application 62/358,958 that day submits, is incorporated by reference and is incorporated herein.
Technical field
The present invention relates to the silicone hydrogels for showing improved biocompatibility.More particularly it relates to by anti- The silicone hydrogels that answering property mixture is formed, the reactive mixture include the mixing for the organosilicon composition that hydroxyl replaces At least one polyamide of object, at least one hydrophilic monomer and at least about 15 weight %.Silicone hydrogels of the invention Show the balance of excellent physics, machinery and biological nature.
Background technique
From at least the 1950s, haptic lens is commercially used utilization just to improve eyesight.First secondary contact lense Piece is made of hard material, therefore is had for user uncomfortable to a certain extent.Contact lens,soft now Piece is then the usually hydrogel made of more soft material.It is proposed soft made of silicone hydrogels connect recently Touch eyeglass.Silicone hydrogels are the water-swelling polymer network with high oxygen transmission degree.These eyeglasses are many lens wearers Good comfort level is provided, but some wearers can not feel like oneself and have excessive eye deposit, cause using these When eyeglass, especially visual acuity is reduced during such as continuous a couple of days (such as up to about 30 days) is worn for a long time.This discomfort And deposit is protein, lipid and mucoprotein by the hydrophobic property of lens surface and these surfaces and eyes and hydrophilic Property surface interaction it is caused.
The approach of water content is to introduce internal wetting agent, such as heavy polymer in a kind of raising silicone hydrogels, It generates more hydrophilic regions and retains more moisture.Introduced internal wetting agent also root Ju form and surface roughness are come Influence the surface lubrication of silicone hydrogels.In poly(vinyl pyrrolidone) (PVP) is used as in silicone hydrogels Wetting agent.For example, United States Patent (USP) 6,367,929,6,822,016 and 7,052,131 is disclosed between 1 weight % and 15 weights Amount between amount % is present in the PVP in reactive monomer mixture.Poly- (N- vinyl-N-methylacetaniide) (PVMA) is non- It is used as internal wetting agent in ionic organosilicon hydrogel.For example, United States Patent (USP) 7,786,185 and 8,022,158 is disclosed between 1 Amount between weight % and 15 weight % is present in the PVMA in reactive monomer mixture.However, not yet disclosing with higher The composition of the internal wetting agent of concentration.Do not disclosed yet internal wetting agent with higher concentration and acceptable physics, machinery and The contact lense of biological nature.
Summary of the invention
The silicone hydrogels with high-content polyamide are prepared for, it is special to show excellent physics, machinery and biology The balance of property.
The present invention relates to a kind of silicone hydrogels formed by reactive monomer mixture, the reactive monomer mixing Object includes: at least one (methyl) acrylic acid hydroxy alkyl ester monomer；The mixture of hydroxyl organosilicon composition；And it is at least one Polyamide.Based on the total weight of reactive component in reactive monomer mixture, polyamide is deposited with the amount greater than 15 weight % It is in reactive monomer mixture.
The invention further relates to the silicone hydrogels formed by reactive monomer mixture, the reactive monomer mixture Include:
A. at least one (methyl) acrylic acid hydroxy alkyl ester monomer；
B. poly- (the two substitution silicon oxygen that at least one first monofunctional hydroxyl with 4 to 8 siloxane repeat units replaces Alkane)；
C. poly- (two replace siloxanes) that at least one second hydroxyl replaces, poly- (two substitutions that second hydroxyl replaces Siloxanes) poly- (two substitutions selected from the monofunctional hydroxyl substitution with 10 to 200 or 10 to 100 siloxane repeat units Siloxanes), the multifunctional hydroxyl with 10 to 200 or 10 to 100 siloxane repeat units replace poly- (two replace silicon oxygen Alkane) and their mixture；
D. the total weight at least at least the one of 15 weight % based on reactive component in the reactive monomer mixture Kind polyamide；And
E. optional other component.
In addition, the present invention provides a kind of method for preparing silicone hydrogels, comprising: preparation is single comprising reactivity below Body mixture: at least one (methyl) acrylic acid hydroxy alkyl ester monomer；The mixture of hydroxyl organosilicon composition；And at least one Kind polyamide and optional other component, wherein the total weight based on reactive monomer mixture, polyamide is to be greater than 15 weights The amount of amount % is present in reactive monomer mixture；And silicone hydrogels are formed by reactive monomer mixture.
These and other embodiment of the invention will become aobvious and easy from exemplary illustration the following description of the present invention See.Specification is not intended to limit the scope of the present invention as defined by claims and its equivalent.The disclosure is not being departed from Innovative content spirit and scope in the case where, it can be achieved that variant of the invention and modification.
Specific embodiment
The present invention provides the silicone hydrogels formed by reactive monomer mixture, the reactive monomer mixture Include: (methyl) acrylic acid hydroxy alkyl ester monomer；Containing organosilicon composition；And at least one polyamide.
Relative to term used in the disclosure, provide defined below.Polymer definition meets by Richard G.Jones,Jaroslav Kahovec,Robert Stepto,Edward S.Wilks,Michael Hess,Tatsuki Kitayama and W.Val Metanomski is edited, the term polymer and name summary that IUPAC in 2008 recommends (Compendium of Polymer Terminology and Nomenclature,IUPAC Recommendations 2008) those of disclosed in.
" about " refer to that number is modified in the range of +/- 5%.For example, phrase " about 10 " will include both 9.5 and 10.5.
Term " (methyl) " refers to that optional methyl replaces.Therefore, such as term nail base of " (methyl) acrylate " Both acrylate group and acrylate group.
No matter where provide chemical structure, it should be understood that disclosed selective over the structure for substituent group Alternative solution can be combined with any combination.Therefore, as fruit structure contains substituent R * and R**, they each contains can Three lists of the group of energy, disclose 9 kinds of combinations.It is equally applicable for the combination of characteristic.
When such as general formula [* * *]nIn " n " subscript when being used to describe the number of repetitive unit in the chemical formula of polymer, should Formula should be construed as indicating the number-average molecular weight of macromolecular.
" macromolecular " is the organic compound that molecular weight is greater than 1500, and can be in reactive or non-reacted.
" polymer " is the macromolecular of the repetition chemical unit of common connection chaining or network structure, and by derivative autoreaction Property mixture in the repetitive unit of included monomer and macromonomer constitute.
" homopolymer " is the polymer made of a kind of monomer or macromonomer；" copolymer " is by two or more Polymer made of monomer, macromonomer or their combination；" terpolymer " be by three kinds of monomers, macromonomer or Polymer made of their combination." block copolymer " is constituted by forming different block or segment.Diblock copolymer There are two blocks for tool.There are three blocks for triblock copolymer tool." pectination or graft copolymer " is by least one macromonomer It is made.
" repetitive unit " or " repeating chemical unit " is that monomer and macromonomer polymerize minimum in generated polymer Repetition atomic group.
" biologic medical equipment " refer to be designed within mammalian tissues or body fluid or on and preferably in people Within body tissue or body fluid or on any product for using.The example of these devices includes but is not limited to wound dressing, sealing Glue, tissue augmentation object, drug delivery system, coating, anti-adhesion barriers, conduit, implantation material, bracket and Ophthalmoligic instrument are (as intraocularly Lens and contact lens).Bio-medical instrument can be Ophthalmoligic instrument, specifically haptic lens, most specifically by organosilicon water-setting Haptic lens made of glue.
" individual " includes people and vertebrate.
" eye surface " includes surface and the glandular epithelium of cornea, conjunctiva, lachrymal gland, accessory lacrimal glands, nasolacrimal duct and Meibomian gland And its top and base portion matrix, puncta and adjacent or relevant structure, including by epithelial cell continuity, innervation with And endocrine system and immune system are connected as the eyelid of function system.
" Ophthalmoligic instrument " refers on intraocular or eye or any device at any position of eyes (including eye surface).This A little devices can provide optical correction, beauty, improve eyesight, treatment effectiveness (being used for example as bandage) or delivering active component, all Such as any combination of drug and class medicament nutrition composition or above-mentioned function.The example of Ophthalmoligic instrument includes but is not limited to eyeglass With optics and ophthalmic insert (including but not limited to Punctal plug etc.)." eyeglass " include Soft contact eyeglass, hard contact eyeglass, It is mixed eyeglass, intraocular lens and covering eyeglass.Ophthalmoligic instrument may include haptic lens.
" haptic lens " refers to the structural body that can be placed on individual eyes cornea, Ophthalmoligic instrument.Haptic lens can mention It delivers for correction, beauty, treatment beneficial effect, including wound healing, active component such as drug or nutrient and healthcare products, is diagnostic Evaluation or monitoring or ultraviolet-resistant and visible light or dazzle reduction or their combination.Haptic lens can be known in the art Any suitable material, and can for soft lens, hard lenses or containing have different characteristics such as modulus, water content, suction The mixing eyeglass of at least two different pieces of light feature or their combination.
In one embodiment, bio-medical instrument of the invention, Ophthalmoligic instrument and eyeglass can be by silicone hydrogels It constitutes.These silicone hydrogels usually contain organosilicon composition and/or hydrophobicity and hydrophilic monomer, the hydrophobicity and parent Aqueous monomers are covalently bonded to one another in cured device.
" silicone hydrogels haptic lens " refers to the haptic lens comprising at least one silicone hydrogel material.It compares In conventional hydrogel, silicone hydrogels haptic lens usually has the oxygen transmission degree of raising.Silicone hydrogels haptic lens benefit Oxygen is transmitted to eyes with both its water and polymer content.
" polymer network " is the macromolecular of crosslinking, it can be swollen, but cannot be dissolved in solvent, because of polymer network A substantially macromolecular." hydrogel " or " hydrogel material " refers to the polymer network under equilibrium state containing water.Water Gel typically contains the water of at least about 10 weight %, or the water of at least about 15 weight %.
" conventional hydrogel " refers to made of the monomer without any siloxy, siloxanes or carbon siloxane group Polymer network.Conventional hydrogel is by mainly containing hydrophilic monomer (such as 2- hydroxyethyl methacrylate (" HEMA "), N- second Vinyl pyrrolidone (" NVP "), N, N- dimethylacrylamide (" DMA ") or vinyl acetate) monomer mixture be made.Beauty State's patent 4,436,887,4,495,313,4,889,664,5,006,622,5,039459,5,236,969,5,270,418,5, 298,533,5,824,719,6,420,453,6,423,761,6,767,979,7,934,830,8,138,290 and 8,389, 597 disclose the formation of conventional hydrogel.Commercially available aqueogel includes but is not limited to etafilcon, polymacon, Wei Fei Health, blunt luxuriant and rich with fragrance health, Lin Nifeikang, hilafilcon, nesofilcon and omafilcon, including they all modifications.
" silicone hydrogels ", which refer to, to be obtained by least one containing organosilicon composition and at least one hydrophilic component copolymerization Hydrogel.Hydrophilic component may also comprise non-reactive polymer.It can be respectively containing organosilicon composition and hydrophilic component single Body, macromonomer or their combination.Contain at least one siloxanes or carbon siloxane group containing organosilicon composition.It is commercially available to have The example of machine silicone-hydrogel include Ba Lafeikang, A Kuafeikang, lotrafilcon, one hundred bright, the delefilcon, enfilcon of view, Fanfilcon, formofilcon, galyfilcon, Sai Nuofeikang, narafilcon, filcon II, asmofilcon A, Samfilcon, riofilcon, stenficlon, somofilcon, and as United States Patent (USP) 4,659,782,4,659,783, 5,244,981、5,314,960、5,331,067、5,371,147、5,998,498、6,087,415、5,760,100、5,776, 999、5,789,461、5,849,811、5,965,631、6,367,929、6,822,016、6,867,245、6,943,203、7, 247,692、7,249,848、7,553,880、7,666,921、7,786,185、7,956,131、8,022,158、8,273, 802、8,399,538、8,470,906、8,450,387、8,487,058、8,507,577、8,637,621、8,703,891、8, 937,110、8,937,111、8,940,812、9,056,878、9,057,821、9,125,808、9,140,825、9156,934、 9,170,349,9,244,196,9,244,197,9,260,544,9,297,928,9,297,929 and WO 03/22321, WO Prepared silicone hydrogels in 2008/061992 and US 2010/048847.Disclosed in these patents and this paragraph All other patent is incorporated by accordingly.
" contain organosilicon composition " refer to containing be in siloxanes [- Si-O-Si] group or carbon siloxane group form at least One silicon-oxygen key monomer, macromonomer, prepolymer, crosslinking agent, initiator, additive or polymer.Group containing organosilicon The example divided includes but is not limited to silicone macromolecule monomer, prepolymer and monomer.The example of silicone macromolecule monomer includes But it is not limited to the dimethyl silicone polymer of the methacrylated with pendant hydrophilic group.It can be used in the present invention Example containing organosilicon composition is found in United States Patent (USP) 3,808,178,4,120,570,4,136,250,4,153,641,4, 740,533、5,034,461、5,962,548、5,244,981、5,314,960、5,331,067、5,371,147、5,760, 100,5,849,811,5,962,548,5,965,631,5,998,498,6,367,929,6,822,016 and 5,070,215 with And European patent 080539.
" reactive mixture " and " reactive monomer mixture ", which refers to, to be mixed and is being subjected to polymeric reaction condition When formed silicone hydrogels and eyeglass of the invention component both (reactivity and non-reacted) mixture.Reaction mixing Object includes reactive component, such as monomer, macromonomer, prepolymer, crosslinking agent, initiator, diluent and additional group Point, such as wetting agent, release agent, dyestuff, light-absorbing compound (such as UV absorbent), pigment, dyestuff and photochromic compound, it Any one of can be reactive, be also possible to non-reacted, but resulting biomedical dress can be retained in In setting；And the active component including drug and class medicament nutrient compounds and any diluent.It should be understood that can be based on made Bio-medical instrument and its desired use and add broad range of additive.The concentration of reactive mixture component is it The weight % shared in all components total amount in addition to diluent in reactive mixture.When a diluent is used, they Concentration be weight % shared by their all components total amounts based on reactive mixture and diluent.
" monomer " is with the non-duplicate reactive group that chain growth polymerization (especially free radical polymerization) can occur Molecule.Certain monomers have the Bifunctionalized dopant that may act as crosslinking agent." macromonomer " is with repetitive structure and energy The linear chain or branched chain polymer of at least one reactive group of chain growth polymerization enough occurs.Monomethyl acryloxypropyl envelope The dimethyl silicone polymer (molecular weight=500-1500g/mol) (mPDMS) and mono- (2- hydroxyl-of the mono- normal-butyl sealing end at end 3- methacryloxypropyl)-propyl it is ether capped mono- normal-butyl sealing end dimethyl silicone polymer (molecular weight=500- 1500g/mol) (OH-mPDMS) is known as macromonomer.In general, the chemical structure of macromonomer is different from target macromolecule Chemical structure, in other words, the repetitive unit of the side group of macromonomer is different from target macromolecule or the repetition list of its main chain Member.
" reactive component " is to become resulting organosilicon water-setting by covalent bonding, hydrogen bonding or formation interpenetrating networks Component in the reactive mixture of a part of the polymer network structure of glue.In general, the chemical structure of macromonomer is not Be same as the chemical structure of target macromolecule, in other words, the repetitive unit of the side group of macromonomer be different from target macromolecule or The repetitive unit of its main chain.It is not reactive component as the diluent and processing aid of a part of polymer architecture.
" polymerizable " means that compound includes at least one reaction that chain growth polymerization such as free radical polymerization can occur Property group.The example of reactive group includes monovalence reactive group listed hereinafter." not polymerizable " means compound not Include such polymerizable groups.
" monovalence reactive group " is that chain growth polymerization can occur, such as free radical polymerization and/or cationic polymerization Group.The non-limiting example of free-radical reactive group includes (methyl) acrylate, styrene, vinyl ethers, (methyl) Acrylamide, N- vinyl lactam, N- vinylamide, O- vinyl carbamate, O- vinylcarbonates, Yi Jiqi Its vinyl groups.In one embodiment, free-radical reactive group includes (methyl) acrylate, (methyl) acryloyl Amine, N- vinyl lactam, N- vinylamide and styryl functional groups, or (methyl) esters of acrylic acid, (methyl) third The mixture of acrylamide and any aforementioned substances.
The example of aforementioned substances includes substituted or unsubstituted C1-6(methyl) alkyl acrylate, C1-6Alkyl (methyl) third Acrylamide, C2-12Alkenyl, C2-12Alkenyl phenyl, C2-12Alkenyl naphthalene, C2-6Alkenyl phenyl C1-6Alkyl, wherein the C1-6On alkyl Suitable substituent group includes ether, hydroxyl, carboxyl, halogen and their combination.
Other polymerization approachs, such as living free-radical polymerization and ionic polymerization can also be used.The monomer for forming device can be formed Gel copolymer.For hydrogel, reactive mixture will generally comprise at least one hydrophilic monomer.
Hydrophilic component is to obtain to clarify single-phase list when mixing with the concentration of 10 weight % with deionized water at 25 DEG C Body.
" interpenetrating polymer networks " or " IPN " is the polymer comprising two or more polymer networks, the polymerization Object network is at least partly interlocked with molecular level, but not covalent bonding and unless chemical bond rupture, otherwise inseparable each other.
" semi IPN " or " half-IPN " be include one or more polymer networks and one or more The polymer of linear chain or branched chain polymer, it is characterised in that at least one network is on molecular scale by least some straight chains or branch Chain infiltration.
" crosslinking agent " is that free radical polymerization can occur at two or more positions of molecule, to form branching-point With the bifunctional or multifunctional component of polymer network.Common example is ethylene glycol dimethacrylate, dimethyl allene Sour tetraethylene glycol ester, trimethylol-propane trimethacrylate, methylene-bisacrylamide, triallyl cyanurate etc..
Phrase " not having surface treatment " means the appearance of the device of the invention (such as silicone hydrogels, haptic lens) Face is not independently processed to improve the wettability of device.The processing that can be carried out in advance includes plasma treatment, transplanting, painting Cloth etc..However, provide the coating such as, but not limited to antimicrobial coatings with characteristic in addition to improved wettability and Coloring or other beauty humidifications can be applied to the device of the invention.
Silicone hydrogels can be formed by reactive monomer mixture, and the reactive monomer mixture includes at least one Hydrophilic monomer, at least one hydroxyl organosilicon composition, at least one crosslinking agent and at least one polyamide.
Polyamide
Reactive monomer mixture includes at least one polyamide.As used herein, term " polyamide " refers to including containing There are the polymer and copolymer of the repetitive unit of amide group.Polyamide may include cyclic amide group, acyclic amide group with And their combination, and can be any polyamide known to those skilled in the art.
Acyclic polyamides include acyclic amide side group and can be in conjunction with hydroxyl groups.Cyclic polyamides include cyclic annular acyl Amine groups and can be in conjunction with hydroxyl group.
The example of suitable acyclic polyamides includes the polymer and copolymer of the repetitive unit comprising Formulas I or Formula II:
Wherein X is direct key ,-(CO)-or-(CO)-NHRe, wherein ReFor C1To C3Alkyl group；RaSelected from H, straight chain Or branch, substituted or unsubstituted C1To C4Alkyl group；RbSelected from H, linear chain or branched chain, substituted or unsubstituted C1To C4 Alkyl group, the amino group with up to two carbon atoms, the amide group with up to four carbon atom and have it is more To the alkoxy base of two carbon-based groups；RcSelected from H, linear chain or branched chain, substituted or unsubstituted C1To C4Alkyl group or Methyl, ethyoxyl, ethoxy and methylol；RdSelected from H, linear chain or branched chain, substituted or unsubstituted C1To C4Alkyl base Group；Or methyl, ethyoxyl, ethoxy and methylol, wherein RaAnd RbIn carbon atom number to be combined be 8 or less, Including 7,6,5,4,3 or less, and wherein RcAnd RdIn carbon atom number to be combined be 8 or less, Including 7,6,5,4,3 or less.RaAnd RbIn carbon atom number be combined can for 6 or less or 4 or Less.RcAnd RdIn carbon atom number be combined can be for 6 or less.As used herein, substituted alkyl group includes quilt Alkyl group replaced amine, amide, ether, hydroxyl, carbonyl, carboxylic group or their combination.
RaAnd RbIt can be independently selected from H, substituted or unsubstituted C1To C2Alkyl group.X can be direct key, and RaAnd Rb It can be independently selected from H, substituted or unsubstituted C1To C2Alkyl group.
RcAnd RdIt can be independently selected from H, substituted or unsubstituted C1To C2Alkyl group, methyl, ethyoxyl, ethoxy, with And methylol.
Acyclic polyamides of the invention may include that the repetitive unit of most Formulas I or Formula II or acyclic polyamides can The repetitive unit of Formulas I or Formula II comprising at least about 50 moles % (including at least about 70 moles of % and at least 80 moles of %).
The specific example of the repetitive unit of Formulas I and Formula II includes being derived from repetitive unit below: N- vinyl-N-methyl Acetamide, N- vinyl acetamide, Ν-vinyl-N-methyl propionamide, N- vinyl-N-methyl -2- methyl propanamide, N- Vinyl -2- methyl-malonamic, N- vinyl-N, N'- dimethyl urea, N, N- dimethylacrylamide, Methacrylamide, And the acyclic amide of formula III a and IIIb:
Acyclic polyamides can also be while include acyclic and cyclic amide repetitive unit copolymer.It can be used to form acyclic The example of the suitable cyclic amide of polyamide includes α-lactams, beta-lactam, gamma-lactam, δ-lactams and the interior acyl of ε- Amine.The example of suitable cyclic amide includes the repetitive unit of formula IV:
Wherein R1It independently is hydrogen atom or methyl；The number that f is 1 to 10, X are direct key ,-(CO)-or-(CO)-NH- Re, wherein ReFor C1To C3Alkyl group.In formula IV, f can be 8 or smaller, including 7,6,5,4,3,2 or 1.In formula IV, F can be 6 or smaller, including 5,4,3,2 or 1.In formula IV, f can be 2 to 8, including 2,3,4,5,6,7 or 8.In formula IV, F can be 2 or 3.
When X is direct key, f can be 2.In the illustration being described, Cyclic polyamides can be poly(vinyl pyrrolidone) (PVP)。
The specific example of the repetitive unit of formula IV includes the repetitive unit derived from n-vinyl pyrrolidone (NVP).
Additional repetitive unit is formed by monomer selected from the following: N- vinylamide, acrylamide, (methyl) acrylic acid The acrylate or methacrylate that hydroxy alkyl ester, (methyl) alkyl acrylate and siloxanes replace.It can be used to form nothing The specific example of the monomer of the additional repetitive unit of ring polyamide includes such as n-vinyl pyrrolidone, N, N- dimethyl allene acyl Amine (DMA), 2-Hydroxyethyl methacrylate, vinyl acetate, acrylonitrile, hydroxy propyl methacrylate, acrylic acid 2- hydroxyl ethyl ester, Methyl methacrylate and butyl methacrylate, methacrylate, GMMA, PEGS etc. and their mixture. It also may include ion monomer.The example of ion monomer includes acrylic acid, methacrylic acid, 2- methacryloxyethyl phosphoric acid Choline, 3- (dimethyl (4- vinyl benzyl) ammonium) propane -1- sulphonic acid ester (DMVBAPS), 3- ((3- acrylamido propyl) Dimethylammonio) propane -1- sulphonic acid ester (AMPDAPS), 3- ((3- methacryiamidopropyl) dimethylammonio) propane -1- Sulphonic acid ester (MAMPDAPS), 3- ((3- (acryloxy) propyl) dimethylammonio) propane -1- sulphonic acid ester (APDAPS), methyl Acryloxy) propyl) dimethylammonio) propane -1- sulphonic acid ester (MAPDAPS), N- (2- carboxyethyl)-N, N- dimethyl -3- [(1- oxo -2- propylene -1- base) amino] -1- propane ammonium inner salt (CBT, carboxybetaine；CAS 79704-35-1), N, N- bis- Methyl-N- [3- [(1- oxo -2- propylene -1- base) amino] propyl] -3- sulfo group -1- propane ammonium inner salt (SBT, sulfobetaines, CAS 80293-60-3), 11 carbon -10- alkene -1- ammonium of 3,5- dioxa -8- azepine -4- phospha, 4- hydroxy-n, N, N- front three Base -9- oxo -4- oxide inner salt (9CI) (PBT, phosphoric acid betaine, CAS163674-35-9).
At least one acyclic polyamides can be selected from polyvinyl Methacrylamide (PVMA), polyvinylacetamide (PNVA), polydimethylacrylamiin (PDMA), polyacrylamide and poly- [N- vinyl N- alkyl acetoacetates amine], wherein N- alkane Base group is selected from containing between (a C1) and five (C5) between carbon atom straight chain and branched alkyl group.
Reactive monomer mixture may include acyclic polyamides and Cyclic polyamides or their copolymer.Acyclic polyamides It can be those any acyclic polyamides as described herein or their copolymer, and Cyclic polyamides can be by individual Formula V Repetitive unit or the repetitive unit of Formula V and any combination of other repetitive units are formed.The example of Cyclic polyamides includes PVP With PVP copolymer.It may also include other polymerization internal wetting agents, such as poly- (ethoxy (methyl) acrylamide).
The total amount of all polyamide is that the total weight based on reactive monomer mixture is greater than 15 in reactive mixture Weight %.In all cases, reactive monomer mixture may include based on reactive component in reactive monomer mixture Total weight is between 15.1 weight % and about 35 weight %, including about 16 weight % to about 30 weight % ranges It is interior, or the polyamide of the amount within the scope of about 20 weight % to about 30 weight %.
Without intending to be bound by theory, polyamide is used as internal wetting agent in resulting silicone hydrogels.This hair Bright polyamide can be to be not polymerizable, and in this case being introduced into silicone hydrogels as semi-intercrossing network.No Polymerizable polyamide is by " retention ", or physically remaines in hydrogel matrix.Alternatively, polyamide of the invention is for example made Be for polyamide macromonomer it is polymerizable, be covalently introduced into silicone hydrogels.Reactive polyamide can quilt Function chemical conversion contains at least one monovalence reactive group.
Polyamide improves the wettability of silicone hydrogels eyeglass without surface treatment.In the organic of the prior art In silicone-hydrogel preparation, due to hydrophobic silicones component and hydrophily and weight average molecular weight is more than that 100,000 dalton is (usual 1,000,000 dalton) wetting agent intrinsic incompatibility, including measure be more than 15% wetting agent it is highly difficult.This is incompatible Property 80 Barres are greater than about for expectation, the preparation of oxygen transmission degree (Dk) of 90 Barres, 100 Barres or 120 Barres especially has challenge Property.Silicone hydrogels can have between 80 and 170 Barres, between 90-170 Barre, 100-170 Barre or 120-170 Dk value between Barre.Inventor is it has surprisingly been found that mixed comprising at least two hydroxy-functional polydialkysiloxanes It closes object and provides the silicone hydrogels with high concentration internal wetting agent He desired Dk value.
When polyamide introduces reactive monomer mixture, weight average molecular weight is at least about 100,000 dalton；It is greater than About 150,000 dalton；Between about 150,000 to about 2,000,000 dalton, between about 300,000 to about 1,800, Between 000 dalton.
Polyamide also may include at least one reactive group.It is the polyamide of 10,000 dalton for molecular weight, it can Including single reaction group.10,000 dalton, greater than about 30,000 dalton are greater than about for molecular weight or are greater than about The polyamide of 100,000 dalton, it may include more than one reactive group.Reactivity and non-reacted polyamide can also be used Mixture.
Polyamide can be introduced into hydrogel by a variety of methods.For example, polyamide can be added in reaction mixture, So that hydrogel polyamide " around " polymerization, formed semi-intercrossing network.
Hydrophilic component
In addition to (methyl) acrylic acid hydroxy alkyl ester monomer described below, reactive monomer mixture also may include selected from parent The additional hydrophilic component of at least one of aqueous monomers and macromonomer.Hydrophilic monomer can be to be known to be used in preparing water Any hydrophilic monomer of gel.The example of suitable hydrophilic monomer family includes: N- vinylamide, N- vinyl acyl Asia Amine, N- vinyl lactam, (methyl) acrylate, (methyl) acrylamide, styrene, vinyl ethers, O- vinyl carbonic acid Ester, O- vinyl carbamate, N- vinyl urea, other hydrophilic ethylene based compounds and their mixture.
The hydrophilic monomer that can be used for preparing Inventive polymers has at least one polymerizable double bond and at least one Hydrophilic functional group.This kind of hydrophilic monomer itself can be used as crosslinking agent, however have more than one polymerizable functionalities when using When the hydrophilic monomer of group, concentration should be limited in level described above, to provide the haptic lens with required elasticity modulus. Term " vinyl " or " containing vinyl " monomer refer to containing vinyl groups (- CH=CH2) monomer, and be usually high anti- Answering property.This kind of hydrophily vinyl-containing monomers known can relatively easily polymerize.
" acrylic compounds " or the monomer of " containing acrylic acid " refer to containing acrylic acid groups (CH2=CRCOX) those of monomer (wherein R is H or CH3, and X is O or N) (it is known that these monomers are easy polymerization), such as N,N-DMAA (DMA), 2-Hydroxyethyl methacrylate (HEMA), glyceral methacrylate, 2- hydroxyethyl methacrylamide, monomethyl third Olefin(e) acid macrogol ester, methacrylic acid, acrylic acid, their mixture etc..
The non-limiting example of hydrophily (methyl) acrylate and (methyl) acrylamide monomer include: acrylamide, N-isopropyl acrylamide, N, N- dimethylaminopropyl (methyl) acrylamide, N, N- dimethylacrylamide (DMA), N- (2- ethoxy) (methyl) acrylamide, N, bis- (2- ethoxy) (methyl) acrylamides of N-, N- (2- hydroxypropyl) (methyl) third Acrylamide, N, bis- (2- hydroxypropyl) (methyl) acrylamides of N-, N- (3- hydroxypropyl) (methyl) acrylamide, N- (2- hydroxyl butyl) (methyl) acrylamide, N- (3- hydroxyl butyl) (methyl) acrylamide, N- (4- hydroxyl butyl) (methyl) acrylamide, vinyl acetate Ester, acrylonitrile and their mixture.
The non-limiting example of hydrophily N- vinyl lactam and N- vinylamide monomers includes: N- vinyl pyrrole Alkanone (NVP), N- vinyl -2- piperidones, N- vinyl -2- caprolactam, N- vinyl -3- methyl -2- caprolactam, N- Vinyl -3- methyl -2- piperidones, N- vinyl -4- methyl -2- piperidones, N- vinyl -4- methyl -2- caprolactam, N- Vinyl -3- ethyl-2-pyrrolidone, N- vinyl -4,5- dimethyl -2-Pyrrolidone, N- vinyl acetamide (NVA), N- vinyl-N-methylacetaniide (VMA), N- vinyl-N-ethyl acetamide, N- vinyl-N-ethyl formamide, N- ethylene Base formamide, N- vinyl-N-methyl propionamide, N- vinyl-N-methyl -2- methyl propanamide, N- vinyl -2- methyl-prop Amide, N- vinyl-N, N '-dimethyl urea, 1- methyl -3- methylene -2-Pyrrolidone, 1- methyl -5- methylene -2- pyrroles Alkanone, 5- methyl -3- methylene -2-Pyrrolidone；1- ethyl -5- methylene -2-Pyrrolidone, N- methyl -3- methylene -2- Pyrrolidones, 5- ethyl -3- methylene -2-Pyrrolidone, 1-N- propyl -3- methylene -2-Pyrrolidone, 1-N- propyl -5- Methylene -2-Pyrrolidone, 1- isopropyl -3- methylene -2-Pyrrolidone, 1- isopropyl -5- methylene -2-Pyrrolidone, N- vinyl-N-ethyl acetamide, N- vinyl-N-ethyl formamide, N- vinyl formamide, N- vinyl isopropyl acyl Amine, N- caprolactam, N- carboxyl vinyl-Beta-alanine (VINAL), N- carboxyl vinyl-α-alanine, N- vinyl miaow Azoles and their mixture.
The non-limiting example of hydrophily O- vinyl carbamate and O- vinylcarbonates monomer includes: N-2- hydroxyl Ethyl vinyl carbamate and N- carboxy-- alanine N- vinyl esters.Hydrophilic vinyl carbonate or carbamic acid The other examples of vinyl acetate monomer are disclosed in United States Patent (USP) 5,070,215, and to be disclosed in the U.S. special for hydrophilic oxazolone monomers In benefit 4,910,277.
Other hydrophilic ethylene based compounds include ethylene glycol vinyl ether (EGVE), two (ethylene glycol) vinyl ethers (DEGVE), allyl alcohol, 2- ethyl oxazoline, vinyl acetate, acrylonitrile and their mixture.
Other suitable hydrophilic monomers will be apparent to those skilled in the art.
Hydrophilic monomer of the invention can for linear chain or branched chain poly(ethylene glycol), poly- (propylene glycol) macromonomer or The random or block copolymer of ethylene oxide and propylene oxide statistically.The macromonomer of these polyethers have one or Multiple reactive groups.The non-limiting example of such reactive group is acrylate, methacrylate, styrene, second Alkene ether, acrylamide, Methacrylamide and other vinyl compounds.In one embodiment, these polyethers Macromonomer includes acrylate, methacrylate, acrylamide, Methacrylamide and their mixture.
The hydrophilic monomer that can be incorporated herein in disclosed polymer can be selected from N, N- dimethylacrylamide (DMA), 2- hydroxyethyl acrylamide, 2- hydroxyethyl methacrylamide, N- hydroxypropyhnethacrylamide, double hydroxyethyl acrylamide, 2,3- bis-hydroxypropyl (methyl) acrylamide, n-vinyl pyrrolidone (NVP), N- vinyl-N-methylacetaniide, N- ethylene Methylacetamide (VMA) and polyethylene glycol monomethacrylate.
Hydrophilic monomer can be selected from DMA, NVP, VMA, NVA and their mixture.
It is not particularly limited typically for the amount of the hydrophilic monomer in the presence of reactive monomer mixture.Hydrophily The amount of monomer can based on desired character of gained hydrogel, including water content, light transmittance, contact angle, protein adsorption rate etc. into Row selection.Based on the total weight of reactive component in reactive monomer mixture, hydrophilic monomer (if present) can be with Within the scope of up to about 40 weight %, 30 weight % or 20 weight %, or about 1 weight % to about 40 weight %, about 1 weight % are extremely Amount within the scope of about 30 weight % or about 1 weight % to about 20 weight % exists.A wonderful effect of the invention exists In the silicone hydrogels with desired wettability, water content and bio-compatible sexual balance can be by containing less than about 30 weights Measure %, less than about 25 weight %；20 weight % or hydrophilic monomer even less than 10 weight %, especially hydrophilic amide list The reaction mixture of body (such as DMA, NVP and VMA) is formed.
Hydroxyl organosilicon composition
Reactive monomer mixture further includes the mixture of the hydroxyl organosilicon composition of different molecular weight or different compositions. First hydroxyl organosilicon composition can be selected from hydroxyl organic silicon monomer, and there is at least four poly- two siloxanes to be replaced to repeat Unit or 4-8 poly- two substitutions siloxane repeat units；And the hydroxyl poly- two of at least one monovalence reactive group replaces Siloxanes.When the first hydroxyl organosilicon composition is hydroxyl siloxanyl monomers, the second hydroxyl organosilicon composition be can be selected from Poly- (two replace siloxanes) that hydroxyl with 4 to 8 siloxane repeat units replaces, have 10 to 200,10 to 100 or 10 Poly- (two replace siloxanes) replaced to the monofunctional hydroxyl of 20 siloxane repeat units, and have 10 to 200 or 10 to Poly- (two replace siloxanes) and their mixture that the multifunctional hydroxyl of 100 siloxane repeat units replaces.When first When hydroxyl organosilicon composition is poly- (two replace siloxanes) that the hydroxyl with 4 to 8 siloxane repeat units replaces, second Hydroxyl organosilicon composition can be selected from the monofunctional hydroxyl with 10 to 200,10 to 100 or 10 to 20 siloxane repeat units Poly- (two replace siloxanes) replaced, and the multifunctional hydroxyl with 10 to 200 or 10 to 100 siloxane repeat units Poly- (two replace siloxanes) that replaces and their mixture.
The hydroxyl organosilicon composition of siloxane repeat unit is replaced not to be all ductility with 4 poly- two in siloxane chain , and there are four repetitive units for tool in each monomer.For having poly- more than four two to replace siloxanes in siloxane chain All hydroxyl organosilicon compositions of repetitive unit, the number of repetitive unit are all ductility, and the peak value being distributed concentrates on The number or so of listed repetitive unit.
Si constituent content in hydroxyl organosilicon composition is that the hydroxyl of greater than about 20 weight % to about 38 weight % have The total molecular weight of machine silicon components.
The example of hydroxyl siloxanyl monomers includes acrylic acid -2- methyl -2- hydroxyl -3- [3- [1,3,3,3- tetramethyl - 1- [(trimethyl silyl) oxygroup] -1- disiloxane base] propoxyl group] propyl ester (" SiGMA ") and 2- hydroxy-3-methyl The compound of (trimethylsiloxy group) silane of acryloxy propoxypropyl-three and Formula V:
Wherein R1For hydrogen atom or methyl group, and R2For the straight chain containing 1 to 8 carbon atom, branch or cyclic alkyl Group or trimethylsiloxy group.
Poly- (two replace siloxanes) that the monofunctional hydroxyl that hydroxyl organosilicon composition can be selected from Formula IV -1 replaces:
Wherein Z is selected from O, N, S or NCH2CH2O, when Z is O or S, R2It is not present；
R1It independently is H or methyl；
R2Straight chain for H or containing one to eight carbon atom, branch or cyclic alkyl radical, any one can be further Replaced by least one hydroxyl group, and it is optionally replaced by amide, ether and their combination；
R3And R4It independently is the straight chain containing one to eight carbon atom, branch or cyclic alkyl radical, any one of them Can further it be replaced by least one hydroxyl group, and it is optionally replaced by amide, ether and their combination；R3 And R4Can be independently selected from methyl, ethyl or phenyl, or can be methyl；
N is the number of siloxane unit, and for poly- (two the replace siloxanes) monomer of the first monofunctional hydroxyl substitution It is 4 to 8, and
R5C selected from linear chain or branched chain1To C8Alkyl group, optionally by one or more hydroxyls, amide, ether, with And their combination replaces.R5It can be the C of linear chain or branched chain4Alkyl, any one of them are optionally optionally substituted by a hydroxyl group, Huo Zheke For methyl.
Poly- (two replace siloxanes) that the monofunctional hydroxyl that hydroxyl organosilicon composition can be selected from Formula IV -2 replaces:
Wherein Z is selected from O, N, S or NCH2CH2O, when Z is O or S, R2It is not present；
R1It independently is H or methyl；
R2Straight chain for H or containing one to eight carbon atom, branch or cyclic alkyl radical, any one can be further Replaced by least one hydroxyl group, and it is optionally replaced by amide, ether and their combination；
R3And R4It independently is the straight chain containing one to eight carbon atom, branch or cyclic alkyl radical, any one of them Can further it be replaced by least one hydroxyl group, and it is optionally replaced by amide, ether and their combination；R3 And R4Can be independently selected from methyl, ethyl or phenyl, or can be methyl；
N is the number of siloxane unit, and poly- (two replace siloxanes) that replaces for the second monofunctional hydroxyl is 10- 200 or 10-100 or 10-50 or 10-20 or 12-18, and
R5C selected from linear chain or branched chain1To C8Alkyl group, optionally by one or more hydroxyls, amide, ether, with And their combination replaces.R5It can be the C of linear chain or branched chain4Alkyl, any one of them are optionally optionally substituted by a hydroxyl group, Huo Zheke For methyl.
The example of simple function hydroxyl organosilicon composition includes mono- (2- hydroxy-3-methyl acryloxypropyl)-propyl The dimethyl silicone polymer (OH-mPDMS) of ether capped mono- normal-butyl sealing end, as shown in Formula VII a, wherein n between 4 and 30, Between 4-8 or 10-20；And the dimethyl silicone polymer with the chemical structure as shown in Formula VII b to VIIId, wherein n is between 4 Between 30,4 and 8 or 10 and 20；n1And n2Independently between 4 to 100；4 to 50；Between 4 to 25；n3For 1-50,1-20 or 1-10；R5C selected from linear chain or branched chain1To C8Alkyl group, optionally by one or more hydroxyls, amide, ether, polyhydroxy Base group replaces, and the polyhydroxy group, which is selected from, has formula CfHg(OH)hLinear chain or branched chain C1To C8Group, wherein f=1-8 And g+h=2f+1, and there is formula CfHg(OH)hCyclic annular C1To C8Group, wherein f=1-8 and g+h=2f-1 and they Combination；Or R5It can be selected from the C that methyl, butyl or hydroxyl replace2-C5Alkyl, including ethoxy, hydroxypropyl, hydroxyl butyl, hydroxyl Amyl and 2,3- dihydroxypropyl；And the poly- carbon siloxanes of Formula IX, wherein for the first hydroxyl organosilicon composition, a is 4-8, and for the second hydroxyl organosilicon composition, a is between 4-100, and R1And R5As defined above.
Poly- (the two substitution silicon oxygen that the second monofunctional hydroxyl of the optional self-drifting VI of second hydroxyl organosilicon composition replaces Alkane), or the compound of the Formula VII a-IX with 10 to 200 siloxane repeat units, and have 10 to 500 or 10 to Poly- (two replace siloxanes) that the multifunctional hydroxyl of the Formula X of 200 or 10 to 100 siloxane repeat units replaces and it Mixture:
Wherein in Formula X, Z is selected from O, N, S or NCH2CH2O；Wherein R1It independently is hydrogen atom or methyl group；For Z =O and S, does not need R2；
R2、R6、R7、R8、R9、R10Independently selected from hydrogen atom or to R11To R14Any substituent group of definition；
R11、R12、R13、R14Independently selected from
Straight chain, branch or cyclic alkyl radical containing one to eight carbon atom, any one of them can be further by least One hydroxyl group, acylamino-, ether, amino, carboxyl, carbonyl group and combination replace；The alkylene oxide group base of linear chain or branched chain Group, especially inferior ethoxyl group [CH2CH2O]p(wherein p is between 1 and 200 or 1 and 100 or 1 and 50 or 1 and 25 or 1 and Between 20), optionally replaced by one or more hydroxyls, amino, acylamino-, ether, carbonyl, carboxyl and their combination；
C1-C6The fluoroalkyl group of linear chain or branched chain, optionally by one or more hydroxyls, amino, acylamino-, ether, Carbonyl, carboxyl and their combination replace；
Substituted or unsubstituted aryl group, especially phenyl group, wherein substituent group be selected from halogen, hydroxyl, alkoxy, The cyclic alkyl radical of alkyl-carbonyl, carboxyl and linear chain or branched chain, can further halogen, hydroxyl, alkoxy, alkyl oxycarbonyl Base and carboxylic group and their combination replace；And
A, b, c, x, y and z are independently between 0 and 100, between 0 and 50, between 0 and 20, between 0 and Between 10 or between 0 and 5；And
N is the number of siloxane repeat unit and is 10 to 500；10 to 200；10 to 100；10 to 50；10 to 20.
Poly- (two replace siloxanes) that poly- (two replace siloxanes) that first monofunctional hydroxyl replaces replaces with the second hydroxyl Weight ratio in the range of 0.1 to 2 or 0.1 to 1.
Hydroxyl organosilicon composition may include the first monofunctional hydroxyl substitution of Formula IV or VIIa-IX (wherein n is 4 to 8) Poly- (two the replace siloxanes) mixture of poly- (two replace siloxanes) that replaces with the second hydroxyl, what second hydroxyl replaced The monofunctional hydroxyl of poly- (two replace siloxanes) selected from Formula IV or VIIa to IX (wherein n is 10-200,10-100 or 10 to 20) Poly- (two replace siloxanes) that the bifunctional hydroxy of poly- (two replace siloxanes) and Formula XI that replace replace,
Wherein
R1It independently is hydrogen atom or methyl group；
R15And R16It independently is the straight chain containing one to eight carbon atom, branch or cyclic alkyl radical, it is any Person can further be replaced by least one hydroxyl group, acylamino-, ether, amino, carboxyl, carbonyl group and their combination； Or independently selected from unsubstituted C1-4Alkyl group and the C replaced by hydroxyl or ether1-4Alkyl group；Or it is selected from methyl, second Base or-(CH2CH2O)mOCH3；
N is selected from 4 to 100；4 to 50；Or 4 to 25；And m is 1-50,1-20 and 1-10.
Example containing multifunctional hydrosiloxane includes α-(2- hydroxyl -1- methacryloxypropoxy propyl)-ω - Those of five siloxanes of butyl-decamethyl and Formula XII:
Wherein Z is selected from O, N, S or NCH2CH2O, when Z is O or S, R2It is not present；R1It independently is H or methyl；R2For H or Straight chain, branch or cyclic alkyl radical containing one to eight carbon atom, any one of them can be further by least one hydroxyls Group replaces, and it is optionally replaced by amide, ether and their combination；And n1And n2Independently between 4 to 100；4 to 50；Between 4 to 25；n3For 1-50,1-20 or 1-10.
The ratio of poly- (two replace siloxanes) that the first hydroxyl organosilicon composition and any of above second hydroxyl replace can In the range of 0.2-1.3,0.4-1 and 0.6-1.
Hydroxyl organosilicon composition is between about 40 weight % and about 70 weight % or about 45 weight % to about 70 weight % Between amount be present in reactive mixture.
Contain organo-silicon compound without hydroxy functional group
Also being included in containing organo-silicon compound without hydroxy functional group is interior.Suitable example includes that of Formula XIII It is a little:
Wherein:
At least one R17For monovalence reactive group, and remaining R17Independently selected from
Monovalence reactive group, monovalent alkyl radical or monovalence aryl group, above-mentioned any group can be also comprising being selected from hydroxyl Base, amino, oxa-, carboxyl, alkyl carboxyl, alkoxy, amide groups, carbamic acid root, carbonate, halogen or their combination Functional group；
Fluoro-alkyl alkyl or aryl group；Partially fluorinated alkyl or aryl group；Halogen；Straight chain, branch or ring-type Alkoxy or aryloxy group；Polyethyleneoxy alkyl group, polypropylene oxygroup alkyl group or the poly- (second of linear chain or branched chain Alkenyloxy group -co- propenyloxy group alkyl) group；And
Monovalence siloxane chain containing the siloxane repeat unit between 1-100, the repetitive unit can also wrap Containing selected from alkyl, alkoxy, hydroxyl, amino, oxa-, carboxyl, alkyl carboxyl, alkoxy, acylamino-, carbamic acid root, halogen Or the functional group of their combination；
Wherein n is 0 to 500 or 0 to 200 or 0 to 100 or 0 to 20, where it is understood that n is crowd when n is not 0 Number (mode) is equal to the distribution of designated value.
In Formula XIII, one to three R17It may include monovalence reactive group.
Suitable univalent alkyl and aryl group include
Unsubstituted and substituted monovalent linear, branch or ring-type C1To C16Alkyl group or unsubstituted monovalence C1To C6Alkane Base group such as replaces and unsubstituted methyl, ethyl, propyl, butyl,
Substituted or unsubstituted C6-C14Aryl group or substituted or unsubstituted C6Aryl group, wherein substituent group include Acylamino-, ether, amino, halogen, hydroxyl, carboxyl, carbonyl group；Or phenyl or benzyl group, their combination etc..
As a R17It is additional to can be selected from the poly- of Formula XIV a or XIVb containing organo-silicon compound when for monovalence reactive group Two replace siloxane macromer；The styryl of Formula XV a or XVb poly- two replaces siloxane macromer or Formula XV c Carbon silane:
Wherein R1For hydrogen atom or methyl；
Z is selected from O, N, S or NCH2CH2O；As Z=O or S, R is not needed2；
Wherein j is the integer between 1 and 20；n1And n2Between 4 to 100；4 to 50；Or between 4 to 25；n3For 1- 50,1-20 or 1-10；Q is up to 50,5-30 or 10-25；
Wherein R18For formula (CH2)rSubstituted or unsubstituted C1-6、C1-4Or C2-4Alkylidene segment, wherein each methylene Group is optionally independent replaced ether, amine, carbonyl, carboxylate, carbamate and their combination；Or alkylene oxides Base segment (OCH2)k, the integer that wherein k is one to three, or wherein R18It can be the mixing of alkylidene and alkylidene oxide segment Object, and the sum of r and k are between 1 and 9；
Wherein each R19It independently is the straight chain containing the carbon atom between one to six, branch or cyclic alkyl base Group, straight chain, branch or cyclic alkoxy group containing the carbon atom between one to six, the poly- sub- second of linear chain or branched chain It is oxygroup alkyl group, phenyl group, benzyl group, substituted or unsubstituted aryl group, fluoroalkyl group, partially fluorinated Alkyl group, perfluoro alkyl group, fluorine atom or their combination；
Wherein R5For the substituted or unsubstituted linear or branched alkyl group containing 1 to 8 carbon atom or 1 to 4 carbon atom Group or methyl or butyl；Or aryl group, any one of them can be replaced by one or more fluorine atoms.
When Z is O, the non-limiting example of polysiloxane macromers includes mono- methacryloxypropyl envelope The dimethyl silicone polymer (mPDMS) of the mono- normal-butyl sealing end at end, as shown in Formula XVI, wherein n is between 3 and 15；Mono- first The poly dimethyl of dimethyl silicone polymer, mono- alkyl sealing end that the mono- alkyl of base acryloxypropyl sealing end blocks, Polyethylene glycol siloxanes, as shown in Formula XVI Ia and XVIIb, wherein n is 4-100,4-20 or 3-15；n1And n2Between 4 to 100；4 to 50；Or between 4 to 25；n3For 1-50,1-20 or 1-10；And there is the knot of the chemistry as shown in Formula XVI IIa to XXIb The macromonomer of structure, wherein R1For hydrogen or methyl group；R2Straight chain for H or containing one to eight carbon atom, branch or ring Shape alkyl group, any one of them can further be replaced by least one hydroxyl group, and its optionally by amide, ether, And their combination replaces；n1And n2Between 4 to 100；4 to 50；Or between 4 to 25；n3For 1-50,1-20 or 1-10；And And R5It can be C1-C4Alkyl or methyl or butyl.
Suitable single (methyl) acryloxyalkyl poly- two replaces the example of siloxanes to include single (methyl) acryloyl-oxy The mono- positive first of the dimethyl silicone polymer of the mono- normal-butyl sealing end of base propyl sealing end, single (methyl) acryloxypropyl sealing end The poly- diethyl silicon for the mono- normal-butyl sealing end that the dimethyl silicone polymer of base sealing end, single (methyl) acryloxypropyl block Oxygen alkane, the polydiethylsiloxane of the mono- positive methyl blocking of single (methyl) acryloxypropyl sealing end, single (methyl) acryloyl Aminoalkyl polydialkysiloxane, single (methyl) acryloxyalkyl sealing end the poly- diaromatic siloxane of monoalkyl and Their mixture.
In Formula XIII, when n is zero, a R18It can be monovalence reactive group, and at least three R18Selected from 1 To the monovalent alkyl radical of the carbon atom of 16,1 to 6 or 1 to 4.The non-limiting example of organosilicon composition includes 3- metering system Acryloxypropylethoxysilane three (trimethylsiloxy) silane (TRIS), 3- methacryloxypropyl-bis- (trimethyl silyls Oxygroup) methyl-monosilane and 3- methacryloxypropyl pentamethyl disiloxane.
The number n of siloxane repeat unit can also be 2 to 50,3 to 25 or 3 to 15；The R of wherein at least one end17Packet Reactive group containing monovalence, remaining R17Selected from the monovalent alkyl radical with 1 to 16 carbon atom, or selected from 1 to 6 The monovalent alkyl radical of a carbon atom.It is 3 to 15 that the silicone compounds of hydroxyl, which not may also comprise wherein n, an end R17 Including monovalence reactive group, another end R17Including the monovalent alkyl radical with 1 to 6 carbon atom, and remaining R17Including those of the monovalent alkyl radical with 1 to 3 carbon atom.The non-limiting example of organosilicon composition includes monomethyl Dimethyl silicone polymer (the M of acryloxypropyl normal-butyl sealing endn=800-1000) (mPDMS, as shown in XXII).
Formula XIII may also comprise such compound: wherein n is 5 to 400 or 10 to 300, two end R17It is monovalence Reactive group, and remaining R17It is independently from each other the monovalent alkyl radical with 1 to 18 carbon atom, this monovalence Alkyl group may have ehter bond between carbon atom, and can also include halogen.
One to four R in Formula XIII17May include the vinylcarbonates or vinyl carbamate of Formula X XIIIa:
Wherein Y represents O-, S- or NH-；R1Represent hydrogen atom or methyl.
Vinylcarbonates or vinyl carbamate monomer containing organosilicon specifically include the bis- [4- (ethylene oxies of 1,3- Base carbonyloxy group) butyl- 1- yl] tetramethyl-disiloxane；3 (ethylene oxy carbonyl sulfenyl) propyl [three (trimethylsiloxies) Silane]；3 [three (trimethylsiloxy) silicyls] allyl carbamates；3 [three (trimethyl silyl oxygen Base) silicyl] propyl vinyl carbamate；Carbonic acid trimethylsilylethyl esters vinyl acetate；Carbonic acid trimethyl first The crosslinking agent of silyl methyl vinyl acetate and Formula X XIIIb.
Wherein in the case where desired biologic medical equipment modulus below with about 200psi, only one R17Including monovalence Reactive group, and remaining R17Being no more than two in group includes monovalent siloxane group group.
Another suitably macromonomer containing organosilicon is the compound of Formula X XIV, and wherein the sum of x and y are 10 to 30 models Enclose interior number.The macromonomer containing organosilicon of Formula X XIV is by making fluoro-ether, hydroxy-end capped dimethyl silicone polymer, different Buddhist Happy ketone diisocyanate and isocyanatoethyl react and are formed.
The not acrylamide silicon oxygen of the not hydroxyl that can be selected from United States Patent (USP) 8,415,405 containing organosilicon composition of hydroxyl Alkane.Other organosilicon compositions suitable for the present invention include those of being described in WO 96/31792, such as contain poly- silicon oxygen Alkane, polyalkylene ether, diisocyanate, poly- fluorohydrocarbon, Polyfluoroether and polysaccharide group macromonomer.It is another kind of suitably to contain Organosilicon composition include by GTP prepare macromonomer containing organosilicon, such as United States Patent (USP) 5,314,960,5,331, 067, those of disclosed in 5,244,981,5,371,147 and 6,367,929.United States Patent (USP) 5,321,108,5,387,662 With 5,539,016 describe the polysiloxanes with polar fluorinated graft or side group, and wherein polar fluorinated graft or side group have The hydrogen atom being connected on two fluorinated carbon atoms of end.US2002/0016383 describes the hydrophily of ether-containing key and siloxanes key Siloxanyl methacrylate and crosslinkable monomers containing polyethers and polysiloxane group.Any above polysiloxanes may be used also As the component containing silicone resin in the present invention.
In an embodiment wherein desirably less than the modulus of about 120psi, organosilicon composition is contained used in eyeglass The major part of mass fraction should be only containing a polymerizable functional group.
The organosilicon composition of hydroxyl not can be selected from the straight of single alkyl sealing end of monomethacrylate acryloxypropylethoxysilane sealing end Chain poly- two replaces siloxanes；Methacryloxypropyl-sealing end straight chain poly- two replaces siloxanes；And their mixing Object.
The not C that the organosilicon composition of hydroxyl is blocked also selected from monomethacrylates1-C4Alkyl-blocked straight chain is poly- Dimethyl siloxane；And their mixture.
In some cases, not the functionalization of hydroxyl containing organosilicon composition can up to about 10 weight % amount use. Example includes being selected from Formula X XII (wherein R5For methyl or butyl) mPDMS, Formula XVI a, XVIIb to XVIIIb, XX, XXIa, Macromonomer shown in the compound and Formula X XV or XXVI (wherein n is 1-50 and m is 1-50,1-20 or 1-10) of XXIb Those of:
Specific example of the functionalization of hydroxyl containing organosilicon composition does not include the mPDMS of Formula XVI Ia, Formula XVI II or XIX (wherein R1For methyl and R5Selected from methyl or butyl) compound and Formula X XV (wherein n is 1-50 or 4-40,4-20) shown in Macromonomer.
Specific example containing organosilicon cross-linking agent includes double methacryloxypropyl dimethyl silicone polymer (wherein n Can be 4-200 or 4-150) and following formula XXVIa-XXVIIc compound, wherein n1And n2Independently selected from 4 to 100；4 To 50；Or 4 to 25；n3For 1-50,1-20 or 1-10, m 1-100,1-50,1-20 or 1-10, and q are up to 50,5-30 Or 10-25；Wherein R1For hydrogen atom or methyl；Wherein Z is selected from O, N, S or NCH2CH2O；As Z=O or S, R is not needed2；R2For H or straight chain, branch or cyclic alkyl radical containing one to eight carbon atom, any one of them can be further by least one Hydroxyl group replaces, and it is optionally replaced by amide, ether and their combination；And wherein each R19Independently For the straight chain containing the carbon atom between one to six, branch or cyclic alkyl radical, contain between one to six Carbon atom straight chain, branch or cyclic alkoxy group, the poly- inferior ethoxyl alkyl group of linear chain or branched chain, phenyl group, Benzyl group, substituted or unsubstituted aryl group, fluoroalkyl group, partially fluorinated alkyl group, perfluoro alkyl group, Fluorine atom or their combination.
The organosilicon composition of hydroxyl can not have the average molecular weight of about 400 dalton to about 4000 dalton.
When it is present, the organosilicon composition of hydroxyl can be do not deteriorate the characteristic of gained eyeglass (including mist degree) Amount exists.The organosilicon composition of hydroxyl can the amount of about 15 weight % or up to about 10 weight % not exist up to.Reactivity Monomer mixture can not include the organosilicon composition of not hydroxyl.Total overall reaction component based on reactive mixture is (e.g., dilute Except releasing agent) meter, containing organosilicon composition (containing hydroxyl and not hydroxyl) can up to about 80 weight %, or about 10 weight % are extremely The amount presence of about 80 weight %, about 20 weight % to about 75 weight %, or about 20 weight % to about 70 weight %.
Charge reactive component
Reactive monomer mixture can be additionally included at least one reactive component electrically charged under physiological condition.Electrification is single Body can be selected from anion, cation, amphoteric ion, glycine betaine and their mixture.
Net negative charge distribution is provided when charge-carrying monomers are in silicone hydrogels incorporated in the present invention.Anionic monomer includes At least one anionic group and at least one reactive group.Specifically, anionic group may include but be not limited to carboxylate radical Group, phosphate radical, sulfate radical, sulfonate radical, phosphonate radical, borate and their mixture.Anionic group may include three to Ten carbon atoms or three to eight carbon atoms.Anionic group may include carboxylic acid group.Specifically, charge-carrying monomers can for selected from Carboxylic monomer below: acrylic acid, methacrylic acid, fumaric acid, maleic acid, itaconic acid, crotonic acid, cinnamic acid, vinyl benzene Formic acid, fumaric acid, maleic acid and itaconic acid monoesters and their mixture.
Charge-carrying monomers can be zwitterionic monomer.Zwitterionic monomer includes at least one amphoteric ion group and at least one A reactive group.As used herein, term " amphoteric ion " refers to the neutral compound with both positive charge and negative electrical charge. Zwitterionic monomer includes glycine betaine monomer.
Charge-carrying monomers can be glycine betaine monomer.Glycine betaine monomer includes at least one betaine group and at least one reaction Property group.As used herein, term " glycine betaine " referred to the positively charged Cationic functional groups such as season without hydrogen atom Ammonium or quaternary phosphine cation and have can not be adjacent to the neutralisation of the negatively charged functional group such as carboxylate group in cationic site Close object.
Charge-carrying monomers include at least one polymerizable groups or reactive group.Reactive group includes that may occur from by base The group of polymerization.The non-limiting example of free-radical reactive group include (methyl) acrylate, styryl, vinyl, Vinyl ethers, (methyl) acrylic acid C1-6Arrcostab, (methyl) acrylamide, C1-6Alkyl (methyl) acrylamide, N- vinyl Lactams, N- vinylamide, C2-12Alkenyl, C2-12Alkenyl phenyl, C2-12Alkenyl naphthalene, C2-6Alkenyl phenyl, C1-6Alkyl, O- Vinyl carbamate and O- vinylcarbonates.
The example of " charge-carrying monomers " include (methyl) acrylic acid, N- [(ethyleneoxy) carbonyl]-Beta-alanine (VINAL, CAS#148969-96-4), 3- acrylamide propionic acid (ACA1), 5- acrylamide propionic acid (ACA2), 3- acrylamido -3- first Base butyric acid (AMBA), 2- (methacryloxy) ethyl-trimethyl salmiac (Q salt or METAC), 2- acrylamide -2- methyl Propane sulfonic acid (AMPS), N- (2- carboxyethyl)-N, N- dimethyl -3- [(1- oxo -2- propylene -1- base) amino] -1- propane ammonium Inner salt (CBT, carboxybetaine；CAS 79704-35-1), N, N- dimethyl-N-[3- [(1- oxo -2- propylene -1- base) ammonia Base] propyl] -3- sulfo group -1- propane ammonium inner salt (SBT, sulfobetaines, CAS 80293-60-3), 3,5- dioxa -8- nitrogen Miscellaneous 11 carbon -10- alkene -1- ammonium of -4- phospha, 4- hydroxy-n, N, N- trimethyl -9- oxo -4- oxide inner salt (9CI) (PBT, Phosphoric acid betaine, CAS 163674-35-9), 2- methacryloxyethyl phosphocholine, 3- (dimethyl (4- vinyl benzyl Base) ammonium) propane -1- sulphonic acid ester (DMVBAPS), 3- ((3- acrylamido propyl) dimethylammonio) propane -1- sulphonic acid ester (AMPDAPS), 3- ((3- methacryiamidopropyl) dimethylammonio) propane -1- sulphonic acid ester (MAMPDAPS), 3- ((3- (acryloxy) propyl) dimethylammonio) propane -1- sulphonic acid ester (APDAPS), methacryloxy) propyl) dimethyl Ammonium) propane -1- sulphonic acid ester (MAPDAPS).
Charge-carrying monomers can be selected from (methyl) acrylic acid, 3- acrylamide propionic acid (ACA1), 5- acrylamide propionic acid (ACA2), And their mixture.
Based on the total weight of reaction monomers mixture, charge-carrying monomers can with up to about 10 weight % (wt.%), including About 0.5 weight % to about 5 weight %, about 0.5 weight % are to about 3 weight %, about 0.5 weight % to about 2 weight %, about 1 weight Measure % to about 10 weight %, about 1 weight % to about 5 weight %, about 1 weight % to about 3 weight %, and about 1 weight % to about 2 Amount within the scope of weight % exists.
(methyl) acrylic acid hydroxy alkyl ester monomer
Reactive mixture of the invention also includes at least one (methyl) acrylic acid hydroxy alkyl ester, wherein hydroxyalkyl group It can be selected from C2-C4The alkyl that list or dihydroxy replace and the poly(ethylene glycol) with 1-10 repetitive unit；Or it is selected from 2- hydroxyl Ethyl, 2,3- dihydroxypropyl or 2- hydroxypropyl.
Suitably the example of (methyl) acrylic acid hydroxy alkyl ester monomer includes (methyl) acrylic acid 2- hydroxyl ethyl ester, (methyl) third Olefin(e) acid 3- hydroxypropyl acrylate, (methyl) acrylic acid 2- hydroxypropyl acrylate, bis- hydroxypropyl acrylate of (methyl) acrylic acid 2,3-, (methyl) acrylic acid 2- hydroxyl fourth Ester, (methyl) acrylic acid 3- hydroxy butyl ester, 1- hydroxypropyl -2- (methyl) acrylate, (methyl) acrylic acid 2- hydroxy-2-methyl third Ester, (methyl) acrylic acid 3- hydroxyl -2,2- dimethyl propyl ester, (methyl) acrylic acid 4- hydroxy butyl ester, (methyl) glycerol acrylate, Polyethylene glycol monomethacrylate and their mixture.
Hydroxyalkyl monomer is also selected from 2-Hydroxyethyl methacrylate, glyceral methacrylate, methacrylic acid 2- hydroxyl Propyl ester, methacrylate, methacrylic acid 3- hydroxyl -2,2- dimethyl propyl ester and their mixture.Hydroxyalkyl Monomer may include 2-Hydroxyethyl methacrylate, methacrylic acid 3- hydroxyl -2,2- dimethyl-propyl ester, hydroxyethyl methacrylate fourth Ester or glyceral methacrylate.
Hydroxyl (methyl) acrylamide is typically too hydrophilic and can not be included as compatibility hydroxyalkyl monomer, and Included the case where for hydrophilic monomer.
The hydroxyalkyl monomer of lower loading may be selected and be less than about 50% or the mist less than about 30% to provide to final eyeglass Angle value.
It should be appreciated that the amount of hydroxy component will change according to Multiple factors, including the hydroxyl group on hydroxyalkyl monomer Number, in amount, molecular weight and presence containing the hydrophily degree of functionality on organosilicon composition.Hydrophilic hydroxy group component can be with up to About 15%, up to about 10 weight %, between about 1 amount % and about 15 weight %, about 3 amount % and about 15 weight %, or about 5 amount % and Amount between about 15 weight % is present in reactive mixture.
Crosslinking agent
Crosslinking agent (also referred to as cross-linking monomer) may include in reactive mixture.Crosslinking agent can be selected from bi-functional linker Agent, trifunctional crosslinking agent, tetrafunctional crosslinking agent and their mixture, including containing organosilicon and without the crosslinking of organosilicon Agent.Crosslinking agent without organosilicon include ethylene glycol dimethacrylate (EGDMA), dimethacrylate, Tetraethylene glycol dimethylacrylate (TEGDMA), trimethylol-propane trimethacrylate (" TMPTMA "), metering system Acid glyceride, 1,3- dimethacrylate；2,3- dimethacrylate；1,6-HD dimethyl propylene Olefin(e) acid ester；1,4- butanediol dimethylacrylate, triallyl cyanurate (TAC), glycerol trimethacrylate, methyl-prop Olefin(e) acid oxygen ethyl vinyl carbonic ester (HEMAVc), allyl methacrylate, methylene-bisacrylamide (MBA), poly- second two Alcohol dimethylacrylate (wherein polyethylene glycol has the up to for example, about molecular weight of 5000 dalton).Crosslinking agent can be usual Amount use, such as about 0.000415 to about 0.0156 mole of every 100 grams of reactive component in the reactive mixture.Alternatively, If hydrophilic monomer and/or containing organosilicon composition because MOLECULE DESIGN or due to dopant due to be it is multi-functional, crosslinking agent is added It is optional to reaction mixture.It may act as crosslinking agent and do not need additional crosslinking agent being added to reaction in the presence case The hydrophilic monomer of mixture and the example of macromonomer include (methyl) acrylate and (methyl) acrylamide sealing end Polyethers.
In addition component
Reactive monomer mixture may include additional component, such as, but not limited to diluent, wetting agent, extinction chemical combination Object, including ultraviolet absorbing agent and photochromic compound；(any one of them can be reactivity for toner, pigment, dyestuff , be also possible to it is non-reacted, but can be retained in bio-medical instrument) and medicament, Antimicrobe compound, medicine Compounds, class medicament nutrient compounds, release agent and their combination.
Diluent classification suitable for silicone hydrogels reaction mixture includes alcohol, tool with 2 to 20 carbon atoms There is the amide derived from primary amine and the carboxylic acid with 8 to 20 carbon atoms of 10 to 20 carbon atoms.Diluent can be primary alconol, secondary The pure and mild tertiary alcohol.
Usually reactive component is blended in diluent, forms reaction mixture.Suitable diluent be this field Know.There is disclosed, their disclosure among WO 03/022321 and US6020445 suitable for the diluent of silicone hydrogels Content is herein incorporated by reference.
Diluent classification suitable for silicone hydrogels reaction mixture includes alcohol with 2 to 20 carbon, has 10 To the amide derived from primary amine and the carboxylic acid with 8 to 20 carbon atoms of 20 carbon atoms.Primary alconol and the tertiary alcohol can be used.It is preferred that Classification includes the pure and mild carboxylic acid with 10 to 20 carbon atoms with 5 to 20 carbon.
Workable specific diluent includes 1- ethyoxyl -2- propyl alcohol, diisopropylaminoethanol, isopropanol, 3,7- bis- Methyl -3- octanol, 1- decyl alcohol, DODECANOL, 1-, 1- octanol, 1- amylalcohol, 2- amylalcohol, 1- hexanol, 2- hexanol, sec-n-octyl alcohol, 3- first Base -3- amylalcohol, tert-pentyl alcohol, the tert-butyl alcohol, 2- butanol, n-butyl alcohol, 2- methyl -2- amylalcohol, 2- propyl alcohol, 1- propyl alcohol, ethyl alcohol, 2- second Base-n-butyl alcohol, bis- (trimethylsiloxy) methyl-monosilanes of (3- acetoxyl group -2- hydroxy propyloxy group)-propyl, the tertiary fourth oxygen of 1- Base -2- propyl alcohol, 3,3- dimethyl -2- butanol, tert-butoxy ethyl alcohol, 2- octyl-DODECANOL, 1-, capric acid, octanoic acid, dodecane Acid, 2- (diisopropylaminoethyl) ethyl alcohol, their mixture etc..
Preferred diluent includes 3,7- dimethyl -3- octanol, DODECANOL, 1-, 1- decyl alcohol, 1- octanol, 1- amylalcohol, 1- Hexanol, 2- hexanol, sec-n-octyl alcohol, 3- methyl -3- amylalcohol, 2- amylalcohol, tert-pentyl alcohol, the tert-butyl alcohol, 2- butanol, n-butyl alcohol, 2- methyl -2- Amylalcohol, 2- ethyl-n-butyl alcohol, ethyl alcohol, 3,3- dimethyl -2- butanol, 2- octyl-DODECANOL, 1-, capric acid, octanoic acid, dodecane Acid, their mixture etc..
Preferred diluent include 3,7- dimethyl -3- octanol, DODECANOL, 1-, 1- decyl alcohol, 1- octanol, 1- amylalcohol, 1- hexanol, 2- hexanol, sec-n-octyl alcohol, DODECANOL, 1-, 3- methyl -3- amylalcohol, 1- amylalcohol, 2- amylalcohol, tert-pentyl alcohol, the tert-butyl alcohol, 2- Butanol, n-butyl alcohol, 2- methyl -2- amylalcohol, 2- ethyl-n-butyl alcohol, 3,3- dimethyl -2- butanol, 2- octyl-DODECANOL, 1-, Their mixture etc..
The mixture of diluent can be used.By the total weight of components whole in reaction mixture, the content of diluent can Equal to up to about 55 weight %.It is highly preferred that diluent is by the total weight of components whole in reaction mixture to be less than about 45 Weight % is used more preferably between about the amount between 15 and about 40 weight %.
If there is diluent, usually the amount of existing diluent is not particularly limited.When a diluent is used, it is based on The total weight of reactive mixture (including reactivity and non-reactive component), diluent can be with about 2 weight % to about 70 Amount within the scope of weight %, including about 5 weight % to about 50 weight %, and within the scope of about 15 weight % to about 40 weight % is deposited ?.
Polymerization initiator can be used in reaction mixture.Polymerization initiator may include generating free radical at a high temperature of appropriateness At least one of lauroyl peroxide, benzoyl peroxide, isopropyl percarbonate, azodiisobutyronitrile etc. and light draw Send out agent system, such as aromatic alpha-hydroxy ketones, alkoxy oxo benzoin, acetophenone, acylphosphine oxide, bis-acylphosphine oxides and Tertiary amine adds diketone, their mixture etc..The illustrative examples of photoinitiator are 1- hydroxycyclohexylphenylketone, 2- hydroxyl -2- Methyl-1-phenyl -propyl- 1- ketone, bis- (2,6- Dimethoxybenzoyl)-2,4-4- trimethylpentylphosphine oxides (DMBAPO), Bis- (2,4,6- trimethylbenzoyl)-phenyl phosphine oxides (Irgacure 819), the oxidation of 2,4,6- trimethyl benzyl diphenyl Phosphine and 2,4,6- trimethyl benzoyl diphenyl base phosphine oxide, benzoin methyl ester and camphorquinone and 4- (N, N- dimethylamino Base) ethyl benzoate composition.
Commercially available visible light initiator systems include819、1700、 1800、819、1850 (derive from Ciba (Ciba Specialty Chemicals)) andTPO initiator (derives from BASF (BASF)).Commercially available ultraviolet initiator includes 1173 Hes2959(Ciba Specialty Chemicals).These and other workable photoinitiator discloses It is rolled up in Section III, Photoinitiators for Free Radical Cationic&Anionic Photopolymerization, second edition, written by J.V.Crivello&K.Dietliker；It is edited by G.Bradley；John Wiley and Sons；New York；In 1998.In the reactive mixture according to cause the reaction mixture photopolymerization it is effective Amount use initiator, such as every 100 parts by weight about 0.1 to about 2 parts by weight of reactive monomer initiator.It can be according to used Initiators for polymerization, use the poly- of the heat or visible light or ultraviolet light or other method initiation reaction mixtures suitably selected Close reaction.Alternatively, initiation can be carried out in the case where not using photoinitiator, for example, electron beam.However, when using photoinitiator When, preferred initiator is bis-acylphosphine oxides, such as bis- (2,4,6- trimethylbenzoyl)-phenyl phosphine oxides (Or 1- hydroxycyclohexylphenylketone and bis- (2,6- Dimethoxybenzoyl) -2,4-4- tri-methyl-amyls 819) The combination of phosphine oxide (DMBAPO), or the method that polymerization causes is via visible-light activated.
The heat or visible light or ultraviolet light or other sides suitably selected can be used according to initiators for polymerization used The polymerization reaction of method initiation reaction mixture.Alternatively, initiation can be carried out in the case where not using photoinitiator, for example, electron beam.
The solidification of organosilicon polymer/hydrogel and the manufacture of eyeglass
Reactive mixture of the invention such as can be shaken or be stirred formation by any method known in the art, and For forming polymer product or device by known method.With or without diluent, by reactive component (hydrophilic monomer, hydroxyl organosilicon composition, crosslinking agent, polyamide etc.) is mixed to form reactive mixture.
For example, silicone hydrogels can be prepared in the following manner: by reactive component and optionally one or more dilute It releases agent to mix with polymerization initiator, and then can be formed by lathe process, cutting etc. by condition appropriate solidification with being formed For the product of suitable shape.Alternatively, reaction mixture can be put into mold, is subsequently cured suitably to make Product.
Reactive mixture of the invention can by for when preparing haptic lens mold reaction mixture it is any Perception method solidification, including rotation mold forming and static casting.Mold forming method is revolved in United States Patent (USP) 3,408,429 and 3,660,545 Disclosed in having, static casting method has disclosed in United States Patent (USP) 4,113,224 and 4,197,266.Haptic lens of the invention It can be formed by directly molding silicone hydrogel, this method was not only economical, but also allowed the final shape of accurate control hydrated lens. For this method, reaction mixture is placed in the mold of the shape with final required silicone hydrogels, mixes reaction Object is subjected to making the condition of monomer polymerization, thus generates the polymer with the approximate shape of final required product.
After solidification, eyeglass can be extracted, to remove unreacted component and eyeglass is made to be detached from lens mold.It extracts Traditional extraction liquid (such as organic solvent of alcohol etc) progress or usable extraction with aqueous solution can be used.
Aqueous solution is the solution comprising water.Aqueous solution of the invention may include the water of at least about 30 weight %, or at least The water of about 50 weight %, or at least about 70% water, or the water of at least about 90 weight %.Aqueous solution also may include additional water-soluble Property component, such as release agent, wetting agent, slip agent, medicament and nutritional drugs component, their combination etc..Release agent is such The mixture of compound or compound: when mixed with water, compared to using the aqueous solution without release agent to be detached from haptic lens The time required to mold, release agent can shorten the time needed for haptic lens break away from moulds.Aqueous solution may include less than about 10 weights The organic solvent such as isopropanol of % or less than about 5 weight % is measured, or can be free of organic solvent.Aqueous solution may not be needed Special disposal, such as purifying, recycling or special disposition process.
In many embodiments, can by (for example) by eyeglass immerse aqueous solution or be exposed in flowing water solution come It realizes and extracts.In various embodiments, extraction may also comprise for example one of following or a variety of: heating aqueous solution；It stirs Mix aqueous solution；The content of demolding aids in aqueous solution is increased to the content for being enough to make eyeglass to be detached from；Machine is carried out to eyeglass Tool or ultrasonic agitation；And filter off at least one in auxiliary agent incorporation aqueous solution, until being enough to promote sufficiently to remove from eyeglass The level of unreacted component.The above operation can carry out in batches or continuously, while be heated, be stirred or both, or not into Row.
Some embodiments may also include application physical agitation, with leaching acceleration and demoulding.For example, can be in aqueous solution Middle vibration or back-and-forth motion adhere to the ophthalmic iens mold section of eyeglass.Other embodiments may include the ultrasound by aqueous solution Wave.
Eyeglass can be sterilized by known way (including but not limited to autoclave sterilization method).
Haptic lens of the invention shows desired mechanical and biological property combination, including water content, mist degree, contact Angle, modulus, oxygen transmission degree, lipid absorptivity, lysozyme absorptivity and PQ1 absorptivity, as shown in the table.Have before all values " about ", and Ophthalmoligic instrument of the invention can have any combination of listed characteristic.
When haptic lens of the invention includes at least one charge-carrying component, lysozyme absorptivity can also be at least about 800 μ G/ eyeglass, or between 50 and 1500 μ g/ eyeglasses, 100-1500 μ g/ eyeglass or 200-1500 μ g/ eyeglass.
Test method
It should be appreciated that all tests as defined in this paper all have a degree of constant error.Therefore, provided in this article As a result it is not construed as absolute number, and should be the numberical range based on the precision specifically tested.
Mist degreeBy at ambient temperature, above flat black background, hydrated test lens being placed on light transmission In borate buffered saline in glass cell, with optical fiber lamp (Dolan-Jenner PL-900 optical fiber lamp, the optical fiber lamps and lanterns Have 0.5 inch diameter light guide) it is illuminated from below with 66 ° of angles perpendicular to eyeglass cell, and with being placed on eyeglass clamper The video camera (equipped with the DVC 1310C RGB video camera or equivalent of appropriate camera zoom lens) of square 14cm is perpendicular to glass Image of the glass cell from top capture testing lens.It is subtracted by using 3.8 software of EPIX XCAP V slow containing borate The image of the blank glass ware of salt water (baseline) is rushed, so that backscatter be subtracted from testing lens scattering.By to test Eyeglass center 10mm is integrated, and is made quantitative analysis for the scattered light image after subduction, is then compared with frosted glass standard Compared with.
Luminous intensity/power setting is adjusted to for the average gray value within the scope of frosted glass standard implementation 900-910；? Under the setting, baseline average gray value is within the scope of 50-70.The average gray value of baseline and frosted glass standard is recorded simultaneously And it is respectively used to the rank of generation 0 to 100.In gray analysis, the flat of baseline, frosted glass and each testing lens is recorded Mean value and standard deviation.For each eyeglass, calculate scaled value according to the following formula: scaled value is equal to average gray value (eyeglass Subtract baseline) divided by average gray value (frosted glass subtracts baseline), multiplied by 100.Three to five testing lens are analyzed, result is asked Average value.
Water contentIt is measured using gravimetry.Balance eyeglass in Wetting Solution 24 hours.It is molten from soaking with cotton swab Each of three testing lens are taken out in liquid, and are placed it on the Water adsorption towel soaked with Wetting Solution.Two of eyeglass Face is all contacted with Water adsorption towel.Testing lens is put into the taring scale pan with tweezers and is weighed.Other two groups of samples are prepared, and are weighed. All wt measurement is triplicate to be carried out, and the average value of those values is for calculating.Weight in wet base is defined as the total of disk and wet eyeglass Weight subtracts the weight of independent weighing pan.
Sample disc is put into and is pre-heated in 60 DEG C of vacuum drying ovens up to 30 minutes, dry weight is measured.Apply vacuum, until obtaining The pressure of at least 1 inch of mercury must be reached.Allow lower pressure.Vacuum valve and pump are closed, eyeglass is at least 12 hours dry； Usually overnight.Vent valve is opened, the nitrogen of dry air or drying is allowed to enter.Baking oven is set to reach atmospheric pressure.Plate is taken out, And it weighs.The total weight that dry weight is defined as disk and dry eyeglass subtracts the weight of independent weighing pan.Test is calculated in accordance with the following methods The water content of eyeglass:
Average value, is recorded as the water content % of testing lens by the average value and standard deviation for calculating water content.
Haptic lensRefractive index(RI) by manual mode or passed through by 500 Abbe refractometer of Leica ARIAS 500 Abbe refractometer of Reichert ARIAS is measured by automatic mode with 100 microns of prism gap.Use deionized water The calibration instrument under 20 DEG C (+/- 0.2 DEG C).It opens prism assemblies and testing lens is placed between the magnetic dot of close to sources Lower prism on.If prism is dry, a few drop salt water are applied to bottom prism.Eyeglass front curve is against bottom prism.So After close prism assemblies.After control is adjusted so that shadow line comes across cross hairs area, refractive index is measured.Five are surveyed Trial lens carries out RI measurement.Five measurements average RI calculated is recorded as refractive index and its standard deviation.
By what is be generally described in ISO 9913-1:1996 and ISO 18369-4:2006, but the pole with following variation Spectrometry measuresOxygen transmission degree(Dk).Measurement is carried out in the environment comprising 2.1% oxygen, which is by being equipped in test chamber Nitrogen under adequate rate and air input create, for example, 1800 ml/mins nitrogen and 200 ml/mins air. T/Dk is calculated using the oxygen concentration of adjusting.Use borate-buffered saline.It is not added by using the pure nitrogen gas environment of humidification MMA eyeglass measures dark current.Eyeglass is not blotted before measuring.Four eyeglasses are stacked, rather than using has with a centimetre survey The eyeglass of the different-thickness (t) of amount.Using curved sensor, rather than flat surface sensor；Radius is 7.8mm.To 7.8mm radius Sensor and 10% (v/v) air-flow calculating it is as follows:
Dk/t=(electric current-dark current of measurement) × (2.97 × 10-8mL O2/(μA-sec-cm2-mmHg)
Marginal correction is related with the Dk of material.
For all Dk values less than 90 Barres:
T/Dk (edge of correction)=[1+ (5.88 × t)] × (t/Dk)
For the Dk value between 90 Barres and 300 Barres:
T/Dk (edge of correction)=[1+ (3.56 × t)] × (t/Dk)
For being greater than the Dk value of 300 Barres:
T/Dk (edge of correction)=[1+ (3.16 × t)] × (t/Dk)
The Dk of non-marginal correction is calculated according to the inverse of the slope of linear regression analysis data acquisition, wherein x variable is Center thickness in centimeters, and y variable is t/Dk value.On the other hand, the slope obtained according to linear regression analysis data Inverse calculate the Dk of marginal correction, wherein x variable is center thickness in centimeters, and y variable is marginal correction T/Dk value.Gained Dk value is recorded as unit of Barre.
It uses deionized water as probe solution at room temperature, is measured using DCA-315 instrument by Wilhelmy plate method EyeglassWettability.In Wetting Solution of the experiment by the way that the eyeglass samples of known parameters to be immersed to known surface tension into Row, while the power being applied on sample because of wetting is measured by sensitive balance.Collected power during being impregnated according to sample Data determine advancing contact angle of the Wetting Solution on eyeglass.Receding contact angle is equally determined by force data, while being taken from liquid Sample out.Wilhelmy plate method is based on following formula: Fg=γ ρ cos θ-B, wherein the wetting power between F=liquid and eyeglass (mg), g =acceleration of gravity (980.665cm/ seconds2), γ=probe liquid surface tension (dyne/cm), the ρ=curved liquid of liquid/eyeglass The perimeter (cm) of haptic lens, θ=dynamic contact angle (degree), and B=buoyancy (mg) at face.When impregnating depth is zero, B is Zero.Four test-strips are cut from the central area of haptic lens.Each width is about 5mm, make its in Wetting Solution into Row balance.Then, each cycles samples four times, and the average value of result is taken, the advancing contact angle and retrogressing for obtaining eyeglass connect Feeler.
Haptic lensMechanical performanceBy using cupping machine, such as equipped with load cell and pneumatic grasping control The Instron model 1122 or 5542 of device processed measures.The eyeglass of the negative one diopter thickness distribution uniform because of its center And it is preferred lens geometry.To have 0.522 inch long, 0.276 inch " ear " wide and 0.213 inch " neck " wide take It is fitted into fixture from the dog bone shape sample slice of -1.00 degree eyeglasses and disconnected to it with the constant strain rate tensile of 2 inch/minutes Until splitting.Before test, with the center thickness of electronic thickness ga(u)ge measurement dog bone samples.Measure the initial gauge length of sample (Lo) length (Lf) when and being broken.At least five samples for measuring every kind of composition, use mean value calculation extension at break hundred Divide ratio: elongation=[(Lf-Lo)/Lo] × 100.
Stretch modulus is calculated as the slope of the initial linear portion of load-deformation curve；Modulus unit is every square of English of pound Very little or psi.Tensile strength is calculated by peak load and initial cross sectional product: tensile strength=peak load is divided by initial cross sectional Product；The unit of tensile strength is psi.
Toughness is calculated by energy to failure and initial sample volume: toughness=energy to failure is divided by initial sample volume；The list of toughness Position is in-lbs/in3。
PQ1 absorptivityIt is measured by chromatography.It is calibrated with the series of standards PQ1 solution with following concentration HPLC:2 μ g/mL, 4 μ g/mL, 6 μ g/mL, 8 μ g/mL, 12 μ g/mL and 15 μ g/mL.Eyeglass is put into 3mL Optifree The polypropylene of Replenish or similar Lens Solution (PQ1 concentration=10 micrograms/mL can be bought from Ai Erkang (Alcon)) connects It touches in eyeglass box.It is also prepared for comprising 3mL solution but is not put into the control lenses box of control lenses.By eyeglass and contrast solution in room Temperature lower storage 72 hours.1mL solution is taken from each sample and control, and is mixed with trifluoroacetic acid (10 μ L).Use HPLC/ ELSD and Phenomenex Luna C5 (4.6mm × 5mm；5 μm of granularities) column, it is analyzed using following equipment and condition: Agilent 1200HPLC or equivalent and ELSD operate in T=100 DEG C, and yield value (Gain)=12, pressure=4.4 bar are filtered Device (Filter)=3s；ELSD parameter can change with instrument difference；Use mobile phase A water (0.1%TFA) and Mobile phase B Acetonitrile (0.1%TFA), column temperature is 40 DEG C and sample volume is 100 μ L.Using elution protocol and it is listed on Table A.Peak area value is made Calibration curve is created for the function construction of PQ1 concentration of standard solution.Then, the quadratic equation of calibration curve is represented by solving To calculate the concentration of PQ1 in sample.Every analysis is carried out to three eyeglasses, results are averaged.PQ1 absorption is recorded as impregnating Percent loss of the PQ1 containing eyeglass relative to the PQ1 in the reference material without eyeglass afterwards.
Table A: HPLC elution protocol
Time (minute) %A %B Flow velocity (mL/min)
0.00 100 0 1.2
1.00 100 0 1.2
5.00 0 100 1.2
8.50 0 100 1.2
8.60 100 0 1.2
11.00 100 0 1.2
The amount of the absorbed cholesterol of haptic lens is measured (in tables of data with LC-MS methodLipid absorptivity).It will Eyeglass is soaked in cholesterol solution, is then extracted with methylene chloride.Heptane/different is evaporated and used to dichloromethane extract Propanol mixture reconstruct, for LC-MS subsequent analysis.As a result the cholesterol micrograms of each eyeglass are recorded as.Deuterated cholesterol Internal standard compound is used to improve the accuracy and precision of this method.
By then using isopropanol in the cholesterol merging 10mL open mouth glass volumetric flask by 15.0 ± 0.5 milligrams, Prepare cholesterol stoste.
Cholesterol soak is prepared as follows: by 0.430 ± 0.010 gram of lysozyme (purity=93%), It, will about in 0.200 ± 0.010 gram of albumin and 0.100 ± 0.010 gram of beta lactoglobulin merging 200mL Glass capacity bottle 190 milliliters of PBS is added to flask, and is vortexed to dissolve content.Then, 2 milliliters of cholesterol stoste and dilute with PBS is added It releases to volume.Volumetric flask is covered and is sufficiently shaken.The concentration of cholesterol soak is about 15 μ g/mL.Note: these are adjusted The quality of component is fluctuated with the purity for considering between-lot, so that aimed concn can be realized.
Six haptic lenses are taken out from its package, the paper handkerchief that can not afford hair is blotted to remove excessive Wetting Solution. Eyeglass is placed in six independent 8mL vials (one eyeglass of each bottle), the cholesterol soak of 3.0mL is added Into each bottle.The New Brunswick Scientific incubator-that bottle capping is placed into 37 DEG C and 100rpm is shaken 72 hours in dynamic device.After incubation, each eyeglass is flushed three times in 100mL beaker with PBS and is placed into 20-mL scintillation vial In.
The methylene chloride of 5mL and the inner mark solution of 100 μ L are added into the scintillation vial respectively comprising eyeglass.It is small minimum 16 When extraction time after, supernatant fluid is transferred in the disposable Glass Culture Tubes of 5mL.The pipe is placed in Turbovap In, make solvent evaporating completely.1mL diluent is placed in culture tube and re-dissolves content.Aforementioned diluent is 70:30 (v/v) heptane and isopropanol mixture.Diluent is also mobile phase.Resulting solution is carefully transferred to automatic sampling bottle In in case LC-MS analyze.
By the way that the deuterated cholesterol (2,2,3,4,4,6-d6- cholesterol) of about 12.5+2mg is weighed 25mL volumetric flask In, it is then diluted with diluent, prepares internal standard stoste.The concentration of internal standard stoste is about 500 μ g/mL.
By the way that the internal standard stoste of 1.0mL to be placed in 50mL volumetric flask, it then is diluted to volume with diluent, prepares internal standard Solution.The concentration of the intermediate inner mark solution is about 10 μ g/mL.
By weighing the cholesterol of about 50+5mg in 100mL volumetric flask, then it is diluted with diluent, preparation ginseng Examine standard stock solution.The concentration for referring to cholesterol in stoste is about 500 μ g/mL.
Then, by the way that the standard solution of appropriate amount to be placed in listed 25-mL, 50-mL or 100-mL volumetric flask, according to 2 preparation work standard solution of table.After standard solution is added to volumetric flask, mixture is diluted to volume with diluent, and And abundant whirlpool.
Table B: Working Standard Solution preparation
Carry out following LC-MS analysis:
(1) 6 times " reference substance 4 " is injected, with evaluation system applicability.The peak area of working stamndard object and internal standard compound RSD% must < 5%, and the RSD (%) of their peak area ratios must < 7% to pass through system suitability.
(2) working stamndard object 1-6 is injected, to create calibration curve.Square (the r of related coefficient2) must > 0.99.
(3) test sample is injected, then injects division criteria object (reference substance 4).The peak area ratio of division criteria object is necessary Within ± the 10% of the average peak area ratio of system suitability injection.
Peak area ratio (reference standard/internal standard compound) value by that will correspond to the concentration of each Working Standard Solution is mapped, Construct calibration curve.The concentration of cholesterol in sample is calculated by solving quadratic equation.Exemplary apparatus for LC-MS analysis And its setting is outlined below and is shown in table C and D.Every time when tuning mass spectrograph, the value of instrument tuner parameters may change.
Turbovap condition:
Temperature: 45 DEG C
Time: 30 minutes or more extremely dry long
Gas: nitrogen@5psi
HPLC condition:
HPLC:Thermo Accela HPLC instrument or equivalent
HPLC column: gilentZorbaxNH2(4.6mm×150mm；5 μm of granularities)
Mobile phase: 70% heptane and 30% isopropanol
Column temperature: 30 DEG C
Sample volume: 25 μ L
Flow velocity: 1000 μ L/min
Table C: Mass Spectrometry Conditions
Table D: tuner parameters
Instrument tuner parameters Value
Discharge current (arbitrary unit): 20
Capillary temperature (DEG C): 240
Gasifier temperature (DEG C) 500
Pipe lens bias (V): 68
Sheath gas pressure (arbitrary unit): 20
Complementary gas stream (arbitrary unit): 15
Haptic lens measures the uptake of lysozyme by HPLC-UV method.Lysozyme absorptivity, which is measured as, to be connect Lysozyme content and eyeglass before touching eyeglass submergence in phosphate buffered saline solution (PBS) is after 37 DEG C submerge 72 hours Test the difference of concentration in solution.
By the way that 0.215 ± 0.005 gram of lysozyme (purity=93%) to be placed in 100mL volumetric flask, then add The PBS of 50mL is then diluted to volume with PBS, prepares lysozyme soak to dissolve lysozyme through being vortexed.It uses Millipore Stericup filter device is filtered/sterilizes to resulting lysozyme soak.Lysozyme soak it is dense Degree is about 2000 μ g/mL.The quality of adjustable lysozyme is fluctuated with the purity for considering between-lot, so that 2000 μ g/mL can be realized Concentration.
Three haptic lenses are taken out from its package, the paper handkerchief that can not afford hair is blotted to remove excessive Wetting Solution. Eyeglass is placed in three independent 8mL vials (one eyeglass of each bottle).The cholesterol soak of 1.5mL is added Into each bottle.Bottle is covered and checks to ensure that each eyeglass is completely immersed in soak.It, will as control sample The lysozyme soak of 1.5mL is added in three independent 8mL vials.Then, under 37 DEG C and 100rpm, make sample It is incubated 72 hours on NewBrunswick Scientific incubator-shaking machine.
By mixing 900mL water, 100mL acetonitrile and 1mL trifluoroacetic acid in 1L vial, diluent is prepared.
By the way that 0.240 ± 0.010 gram of lysozyme (purity=93%) to be placed in 100mL volumetric flask, later with dilution Dilution agent prepares lysozyme stoste to volume.The concentration of lysozyme stoste is about 2200 μ g/mL.
As shown in table E, the lysozyme stoste of appropriate amount is mixed with diluent using 5mL volumetric flask, prepares a series of works Make standard solution.
Table E: working stamndard object
By the way that the trifluoroacetic acid of 1mL to be added in 10mL Glass capacity bottle, then it is diluted, is prepared with HPLC water 10% (v/v) solution.Sample for HPLC-UV analysis is prepared as follows: (1) by by the test sample of 1000 μ L and 10 μ L 10%TFA solution be placed in automatic sampling bottle in, or (2) pass through the reference standard of the reference standard of 1000 μ L and 10 μ L is dilute It releases in agent merging automatic sampling bottle.
The analysis involves the steps of:
(1) 6 times " reference substance 4 " is injected, with evaluation system applicability.Peak area and the RSD% of retention time must < 0.5%, to pass through system suitability.
(2) working stamndard object 1-6 is injected, to create calibration curve.Square (the r of related coefficient2) must > 0.99.
(3) test sample is injected, then injects division criteria object (reference substance 4).The peak area of division criteria object is necessary for ± the 1% of the average peak area of system suitability injection.
By the way that the peak area value mapping of the concentration of each lysozyme Working Standard Solution will be corresponded to, calibration curve is constructed.It is logical Cross the concentration for solving linear equation to calculate lysozyme in test sample.Typical equipment and its setting are outlined below or be shown in table In F.
Instrument: Agilent 1200HPLC has UV detection (or equivalent form HPLC-UV)
Detection: UV@280nm (5nm bandwidth)
HPLC column: Phenomenex Luna C5 (50 × 4.6mm) or Agilent PLRP-S (50 × 4.6mm)
Mobile phase A: H2O (0.1%TFA)
Mobile phase B: acetonitrile (0.1%TFA)
Column temperature: 40 DEG C
Sample volume: 10 μ L
Table F:HPLC service condition
Time (minute) %A %B Flow velocity (mL/min)
0.0 95 5 1.2
4.0 5 95 1.2
4.1 95 5 1.2
6.5 95 5 1.2
Alternatively, lysozyme absorptivity is measured as described below.It is being supplemented with 1.37g/L sodium bicarbonate and the Portugal 0.1g/L D- In the phosphate buffer of grape sugar, lysozyme soln is prepared by Egg-white (Sigma, L7651) with the concentration of 2mg/mL.
Three eyeglasses of each test sample are used for using the test of each protein solution, and use PBS molten as compareing Liquid tests three eyeglasses.Testing lens is blotted on sterile gauze to remove Wetting Solution and be sterilely transferred to using sterility forceps Sterile each groove includes on 24 groove tissue culture plates of the lysozyme soln of 2mL (one eyeglass of each groove).Respectively A eyeglass is completely immersed into solution.As control, the lysozyme soln of 2mL is placed in a groove without haptic lens.
Plate is sealed to prevent to evaporate and be dehydrated using paraffin wax film, and is placed on rail mounted oscillator and at 35 DEG C It is incubated 72 hours with the stirring of 100rpm.After 72 hours incubation periods, eyeglass is rushed by impregnating eyeglass into the PBS of 200mL It washes 3 to 5 times.The moisture absorption on paper handkerchief by eyeglass, removes excessive PBS, and is transferred into sterile conical tubes (1 in each pipe Eyeglass) in, it include a certain amount of PBS in each pipe, the amount of PBS is the estimated value according to the lysozyme absorbed (according to each The composition of eyeglass is estimated) determine.Measured lysozyme concentration is intended in each pipe must be in the white egg as described in manufacturer Within the scope of white reference substance (0.05 microgram to 30 micrograms).Known each eyeglass is absorbed to the sample dilution 5 of the 100 following lysozymes of μ g Times.The sample that known each eyeglass absorbs the 500 above lysozymes of μ g is diluted 20 times.
Lysozyme absorptivity is measured using the bicinchoninic acid method on eyeglass, and the method uses QP-BCA kit (Sigma, QP-BCA), it then follows the step as described in manufacturer, and the eyeglass by soaking from lysozyme soln is surveyed Fixed optical density subtracts optical density measured by the eyeglass soaked in PBS and is calculated.Optical density use can be at 562nm Read the Synergy II microplate measurement of optical density.
The present invention is described in conjunction with following instance now.Before describing multiple exemplary implementation schemes of the invention, It should be appreciated that the present invention is not limited to structure details and process mentioned in being described below.The present invention can have other realities Scheme is applied, and can be practiced or carried out in many ways.
Following abbreviation will be used in embodiment, they have following meanings:
BC: rear curved surface plastic mould
FC: front curve plastic mould
NVP:N- vinyl pyrrolidone (Acros or Aldrich)
DMA:N, N- dimethylacrylamide (Jarchem)
HEMA: 2-Hydroxyethyl methacrylate (Bimax)
NMMA:N- methyl methacrylamide (Monomer Polymer)
VMA:N- vinyl-N-methylacetaniide (Aldrich)
AA: acrylic acid
MAA: methacrylic acid (Acros)
VINAL:N- [(ethyleneoxy) carbonyl]-Beta-alanine；CAS#148969-96-4
ACA1:3- acrylamide propionic acid
ACA2:5- acrylamide propionic acid
In CBT:N- (2- carboxyethyl)-N, N- dimethyl -3- [(1- oxo -2- propylene -1- base) amino] -1- propane ammonium Salt；Carboxybetaine；CAS 79704-35-1
In SBT:N, N- dimethyl-N-[3- [(1- oxo -2- propylene -1- base) amino] propyl] -3- sulfo group -1- propane ammonium Salt；Sulfobetaines；CAS 80293-60-3
11 carbon -10- alkene -1- ammonium of PBT:3,5- dioxa -8- azepine -4- phospha, 4- hydroxy-n, N, N- trimethyl -9- Oxo -4- oxide inner salt (9CI)；Phosphoric acid betaine；CAS 163674-35-9
Q salt or METAC:2- (methacryloxy) ethyl-trimethyl salmiac
AMPS:2- acrylamide-2-methylpro panesulfonic acid
HPMA: methacrylic acid 2- hydroxypropyl acrylate
HEAA: acrylic acid 2- hydroxyl ethyl ester
Bis- (2- ethoxy) acrylamides of Bis-HEAA:N, N-
GMMA: methacrylic acid 2,3- bis- hydroxypropyl acrylate
HBMA: methacrylic acid 2- hydroxy butyl ester
Blue HEMA:1- amino -4- [3- (4- (2- methacryloxy-ethyoxyl) -6- chlorotriazine -2- base amino) - 4- sulfophenyl amino] anthraquinone-2-sulfonic acid, such as United States Patent (USP) 5, described in 944,853
PVMA: poly- (N- vinyl N- methylacetamide) Mw=570KDa or 628KDa
PVP: poly- (n-vinyl pyrrolidone) (ISP Ashland) K90
EGDMA: ethylene glycol dimethacrylate (Esstech)
TEGDMA: tetraethylene glycol dimethylacrylate (Esstech)
TMPTMA: trimethylol-propane trimethacrylate (Esstech)
TAC: triallyl cyanurate (Polysciences)
MBA: methylene-bisacrylamide (Aldrich)
2250: two acryloxy dimethyl silicone polymer (Evonik) of TegomerV-Si
Irgacure 819: bis- (2,4,6- trimethylbenzoyl) phenyl phosphine oxide (BASF or Ciba Specialty Chemicals)
Irgacure 1870: bis- (2,6- Dimethoxybenzoyl) -2,4,4- trimethyl-pentyl phosphine oxides and 1- hydroxyl Base-cyclohexyl-phenyl -one blend (BASF or Ciba Specialty Chemicals)
MPDMS: the dimethyl silicone polymer (800- of single normal-butyl sealing end of monomethacrylate acryloxypropylethoxysilane sealing end 1000MW)(Gelest)
HO-mPDMS: the ether capped mono- normal-butyl sealing end of mono- (2- hydroxy-3-methyl acryloxypropyl)-propyl Dimethyl silicone polymer (400-1000MW) (Ortec or DSM-Polymer Technology Group)
TRIS:3- methacryloxypropyl three (trimethylsiloxy) silane
SiMAA:2- acrylic acid, 2- methyl -2- hydroxyl -3- [3- [1,3,3,3- tetramethyl -1- [(trimethyl silyl) Oxygroup] disiloxane base] propoxyl group] propyl diester (Toray)
SA2:N- (2,3- dihydroxypropyl) N- (3- tetra- (dimethyl silane oxygroup) dimethyl butyrate base silane) propyl) third Acrylamide
MPEG 950: polyethylene glycol monomethacrylate (Aldrich)
D3O:3,7- dimethyl -3- octanol (Vigon)
TAM: tert-pentyl alcohol (BASF)
3E3P:3- ethyl 3- amylalcohol
DI water: deionized water
IPA: isopropanol
Norbloc:2- (2'- hydroxy-5-methyl base acryloyl-oxyethyl phenyl) -2H- benzotriazole (Janssen)
PP: polypropylene, the i.e. homopolymer of propylene
TT:Tuftec, i.e. hydrogenated styrene butadiene block copolymer (Asahi Kasei Chemicals)
Z:Zeonor, i.e. polycyclic alkene thermoplastic polymer (Nippon Zeon Co Ltd)
Embodiment
The preparation of poly- (N- vinyl N- methylacetamide) (pVMA): by 380mL (3.48mol) through distilling N- ethylene The azodiisobutyronitrile of base-N- methylacetamide and 187mg (1.14mmol) be added to equipped with reflux condenser, magnetic stir bar and In 3 neck round-bottom flasks of thermocouple, and nitrogen bubbling is made to remove oxygen by reaction mixture 2 hours.Then, reaction is mixed It closes object to heat 24 hours in 75 DEG C, reaction mixture is cured during this period.Reaction product is quenched in air, and is passed through Last handling process 1 or last handling process 2 are separated.Last handling process 1: reaction product is made to be dissolved in the two of 800mL in 40 DEG C In chloromethanes and it is cooled to room temperature.Under manual agitation, solution is poured into 2L ice ether, is obtained after the solvent that inclines white Color solid.It is air-dried solid product, is then dried in vacuum overnight at 50 DEG C.The product being settled out is milled into white thin Powder is simultaneously dried in vacuum overnight (85% yield) in 50 DEG C.Last handling process 2: reaction product is made to be dissolved in the water and in dialysis membrane tube It sufficiently dialyses in (Spectra Pore MWCO 3500), and be freeze-dried (LABCONCO,TriadTMFreezing Drying system, model #7400030) or spray drying (BUCHI disk-type spray dryer, model #B-290).Molecular weight size Exclusion chromatography and multi-angle light scattering (SEC-MALS) are measured.SEC-MALS setting (contains 10mM using methanol LiBr mobile phase (50 DEG C, flow velocity 0.6mL/min)) are used as.It is solidifying using three concatenated Tosoh Biosciences TSK- Rubber column gel column [SuperAW30004um, 6.0mm ID × 15cm (PEO/DMF exclusion limit=60,000g/ mole), SuperAW40006um, 6.0mmID × 15cm (PEO/DMF exclusion limit=400,000g/ mole) and SuperAW50007um, 6.0mm ID × 15cm (PEO/DMF exclusion limit=4,000,000g/ moles)], with online Agilent 1200UV/VIS Diode array detector, Wyatt Optilab rEX interfere formula refractometer and Wyatt miniDAWN Treos multi-angle Laser light scattering (MALS) detector (λ=658nm).D η/dc value of 0.1829mL/g is for absolutely dividing under 30 DEG C (λ=658nm) Son measures fixed.Absolute molecular weight and polydispersity are calculated with Wyatt ASTRA 6.1.1.17SEC/LS software package.Divide equally again Son amount usually changes in about 500KDa between about 700KDa, and polydispersity changes between about 1.8 to about 2.8.
Embodiment 1-15
Each reactive mixture is formed as follows: being mixed reactive component listed by table 1 and 2, is not added using heating or The stainless steel or glass syringe of heat make it be filtered through 3 μm of filters, then apply vacuum about 10-20 points at ambient temperature Clock is de-gassed.In the glove box with nitrogen atmosphere and less than 0.1% oxygen, Eppendorf pipette is used at room temperature It will be in FC made of the reactive mixture dosing to Zeonor of about 75-100 μ L.Then, the Z:PP of 55:45 (w/w) is blended BC made of object is placed on FC.Before dosing, balance mold in glove box at least 12 hours.By eight pallets (respectively containing eight such die assemblies) is placed on plating filmed metals plate, and quartz plate is placed in tray top to keep suitable When cooperation and alignment.Plate is transferred in the adjacent gloves case for being maintained at 60-65 DEG C, use intensity 4-5mW/cm2's TL03 illumination solidifies eyeglass 20 minutes from top.Highly viscous reactive monomer mixture dosing will be shown at room temperature to arrive In the mold for heating glove box.Light source is in above pallet at about six inches.The detailed description of curing method and equipment is found in United States Patent (USP) 8,937,110.
To eyeglass hand-stripping, and most of lens sticks are in FC and by making about 64-112 eyeglass be suspended in about one It about one hour in the 70%IPA risen, is then washed with 25%IPA, is washed twice with DI, finally use boric acid salt buffer Wetting Solution It washes twice and separates.Each washing step continues between 10 minutes and 30 minutes.Laboratory level eyeglass is detached from usual It is carried out in the wide-mouth bottle on the roller of laboratory.Those skilled in the art recognize, with regard to isopropanol water solution concentration, use The number of each solvent washing and for the duration of each step, exact eyeglass be detached from process can according to lens formulation and Moulding material and change.The purpose that eyeglass is detached from process is to be detached from all eyeglasses and zero defect, from the net of dilution solvent swell Network is changed into the hydrogel of Wetting Solution swelling.Eyeglass is transferred in bottle, is then carried out within high pressure sterilization 30 minutes with 122 DEG C Sterilizing.The physical and mechanical property of measurement sterile lens is listed in table 3.
Table 1
Table 2
Table 3
Embodiment 1-15 is by (having 4 with 3 weight % to 30 weight %PVP and two kinds of hydroxy-functional organosilicon compositions Haptic lens is prepared with the preparation of the mixture of the HO-mPMDS of 15 repetitive units).Mirror with 15-30 weight %PVP Piece shows 16% or smaller haze value, this is far superior to haze value shown in comparative example 3-5.Embodiment 7-13 also shows institute The low advancing contact angle (9 ° -63 °) and desired other characteristics needed (including water content, modulus, Dk and lipid absorptivity) Balance.In view of the hydrophilic monomer (DMA) that these preparations include less than 15 weight %, this is especially wondrous.
Embodiment 5 (including SiMAA rather than HO-mPDMS, n=4) is compared with embodiment 6, embodiment 6 shows Dk Value is than embodiment 5 high 50% (158 Barres are compared to 104 Barres), and modulus value is lower (106psi is compared to 132psi), together When keep similar water content, mist degree and contact angle values.
Embodiment 16-24
Each reactive mixture is formed as follows: make reactive component listed by table 4 mix, using heating or it is unheated Stainless steel or glass syringe make it be filtered through 3 μm of filters, then apply at ambient temperature vacuum about 10-20 minutes into Row degassing.It, at room temperature will about with Eppendorf pipette in the glove box with nitrogen atmosphere and less than 0.1% oxygen In FC made of the reactive mixture dosing to Zeonor of 75-100 μ L.Then, by the Z:PP blend system of 55:45 (w/w) At BC be placed on FC.Before dosing, balance mold in glove box at least 12 hours.(respectively by eight pallets Include eight such die assemblies) it is placed on plating filmed metals plate, and quartz plate is placed in tray top to keep appropriate Cooperation and alignment.Plate is transferred in the adjacent gloves case for being maintained at 60-65 DEG C, use intensity 4-5mW/cm2TL03 light According to, from top make eyeglass solidify 15 minutes.Highly viscous reactive monomer mixture dosing will be shown at room temperature to heating hand In the mold of casing.Light source is in above pallet at about six inches.It is special that the detailed description of curing method and equipment is found in the U.S. Benefit 8,937,110.
To eyeglass hand-stripping, and most of lens sticks are in FC and by making about 64-112 eyeglass be suspended in about one It about one hour in the 70%IPA risen, is then washed with 25%IPA, is washed twice with DI, finally use boric acid salt buffer Wetting Solution It washes twice and separates.Each washing step continues between 10 minutes and 30 minutes.Eyeglass is detached from usually in laboratory It is carried out in wide-mouth bottle on roller.Those skilled in the art recognize, wash with regard to the concentration of isopropanol water solution, with each solvent For the duration of the number and each step washed, exact eyeglass is detached from process can be according to lens formulation and moulding material And change.The purpose that eyeglass is detached from process is to be detached from all eyeglasses and zero defect, be changed into from the network of dilution solvent swell The hydrogel of Wetting Solution swelling.Eyeglass is transferred in bottle, is then sterilized within high pressure sterilization 30 minutes with 122 DEG C.It surveys The physical and mechanical property of amount sterile lens is listed in table 5.
Table 4
Table 5
The preparation of embodiment 16 to 24 show be prepared for showing acceptable mist degree and contact angle have 15% or more The eyeglass of PVP.
Embodiment 25-33
Each reactive mixture is formed as follows: make reactive component listed by table 6 mix, using heating or it is unheated Stainless steel or glass syringe make it be filtered through 3 μm of filters, then root Ju reactive mixture viscosity, at ambient temperature Apply vacuum about 10-60 minutes and is de-gassed.In the glove box with nitrogen atmosphere and less than 0.1% oxygen, at room temperature It will be in FC made of the reactive mixture dosing to Zeonor of about 75-100 μ L with Eppendorf pipette.Then, by 55: BC made of the Z:PP blend of 45 (w/w) is placed on FC；Alternatively, it can be used by 90:10 (w/w) Z:PP or only by PP system At FC and BC.Before dosing, balance mold in glove box at least 12 hours.Eight pallets (are respectively contained eight A such die assembly) be placed on plating filmed metals plate, and quartz plate is placed in tray top with keep cooperation appropriate and Alignment.Plate is transferred in the adjacent gloves case for being maintained at 60-65 DEG C, use intensity 3-4mW/cm2TLO3 light bulb, from top Portion solidifies eyeglass 15 minutes.Mould of the highly viscous reactive monomer mixture dosing to heating glove box will be shown at room temperature In tool.Light source is in above pallet at about six inches.The detailed description of curing method and equipment is found in United States Patent (USP) 8,937, 110。
To eyeglass hand-stripping, and most of lens sticks are in FC and by making about 64-112 eyeglass be suspended in about one It about one hour in the 70%IPA risen, is then washed with 70%IPA, is washed twice with DI, finally use boric acid salt buffer Wetting Solution It washes twice and separates.Each washing step continues between 10 minutes and 30 minutes.Eyeglass is detached from usually in laboratory It is carried out in wide-mouth bottle on roller.Those skilled in the art recognize, wash with regard to the concentration of isopropanol water solution, with each solvent For the duration of the number and each step washed, exact eyeglass is detached from process can be according to lens formulation and moulding material And change.The purpose that eyeglass is detached from process is to be detached from all eyeglasses and zero defect, be changed into from the network of dilution solvent swell The hydrogel of Wetting Solution swelling.Eyeglass is transferred in bottle, is then sterilized within high pressure sterilization 30 minutes with 122 DEG C.It surveys The physical and mechanical property of amount sterile lens is listed in table 7.
The preparation of embodiment 25 to 33 show be prepared for showing acceptable mist degree and contact angle have 15% or more The eyeglass of pVMA, but these eyeglasses are not as good as wettable comprising PVP rather than the similar eyeglass of pVMA.
Table 6
Table 7

Claims (54)

1. a kind of silicone hydrogels formed by reactive monomer mixture, the reactive monomer mixture includes:
A. at least one (methyl) acrylic acid hydroxy alkyl ester monomer；
B. poly- (two replace siloxanes) that at least one first monofunctional hydroxyl with 4 to 8 siloxane repeat units replaces；
C. poly- (two replace siloxanes) that at least one second hydroxyl replaces, poly- (the two substitution silicon oxygen that second hydroxyl replaces Alkane) poly- (the two substitution silicon oxygen selected from the monofunctional hydroxyl substitution with 10 to 200 or 10 to 100 siloxane repeat units Alkane), the multifunctional hydroxyl with 10 to 200 or 10 to 100 siloxane repeat units replace poly- (two replace siloxanes), And their mixture；
D. the total weight at least at least one of 15 weight % based on reactive component in the reactive monomer mixture is poly- Amide；And
E. optional other component.
2. silicone hydrogels according to claim 1, wherein based on all reactions in the reactive monomer mixture Property component total weight, the polyamide between 15.1 weight % and about 40 weight % or between 15.1 weight % and Amount between about 30 weight % is present in the reactive mixture.
3. silicone hydrogels according to claim 1 or 2, wherein in the polyamide-based sheet selected from Cyclic polyamides, Acyclic polyamides and their mixture.
4. silicone hydrogels according to claim 3, wherein the polyamide includes selected from Formulas I, Formula II and formula IV Repetitive unit:
Wherein
R1It independently is hydrogen atom or methyl；
X is direct key ,-(CO)-or-(CO)-NH-Re, wherein ReFor C1To C3Alkyl group；
RaSelected from H, linear chain or branched chain, substituted or unsubstituted C1To C4Alkyl group；
RbSelected from H, linear chain or branched chain, substituted or unsubstituted C1To C4Alkyl group, the amino with up to two carbon atoms Group, the amide group with up to four carbon atom and the alkoxy base with up to two carbon-based groups；
RcSelected from H, linear chain or branched chain, substituted or unsubstituted C1To C4Alkyl group；
RdSelected from H, linear chain or branched chain, substituted or unsubstituted C1To C4Alkyl group；
Wherein RaAnd RbIn carbon atom number to be combined be 8 or less, and wherein RcAnd RdIn carbon atom number close one Rise is 8 or less.
5. silicone hydrogels according to claim 4, wherein RaAnd RbIn carbon atom number be combined as 6 or more It is few.
6. silicone hydrogels according to claim 3, wherein the Cyclic polyamides by α-lactams, beta-lactam, The preparation of at least one of gamma-lactam, δ-lactams and ε-lactams.
7. silicone hydrogels according to claim 3, wherein the Cyclic polyamides include the repetitive unit of formula IV:
Wherein
R1It independently is hydrogen atom or methyl；The number that f is 1 to 10, and
X is direct key ,-(CO)-or-(CO)-NH-Re, wherein ReFor C1To C3Alkyl group.
8. silicone hydrogels according to claim 7, wherein f is 8 or smaller.
9. silicone hydrogels according to claim 8, wherein f is 6 or smaller.
10. silicone hydrogels according to claim 7, wherein f is 2 to 6.
11. silicone hydrogels according to claim 10, wherein f is 3.
12. silicone hydrogels according to claim 10, wherein f is 2.
13. silicone hydrogels according to claim 3, wherein the polyamide is copolymer.
14. silicone hydrogels according to claim 1, wherein the polyamide is selected from polyvinylpyrrolidone (PVP), vinyl methylacetamide (PVMA), polydimethylacrylamiin (PDMA), polyvinylacetamide (PNVA), poly- (ethoxy (methyl) acrylamide), polyacrylamide and their copolymer and mixture.
15. silicone hydrogels according to claim 14, wherein the polyamide is PVP.
16. silicone hydrogels according to claim 14, wherein the polyamide is PVMA.
17. silicone hydrogels according to claim 13, wherein the copolymer includes being selected from least 80 moles of % Repetitive unit below: NVP, VMA, DMA, NVA and their mixture.
18. silicone hydrogels according to claim 13, wherein the copolymer also includes selected from the following at least one Kind repetitive unit: N- vinylamide, acrylamide, (methyl) acrylic acid hydroxy alkyl ester, (methyl) alkyl acrylate, N- second Vinyl pyrrolidone, N, N- dimethylacrylamide, 2-Hydroxyethyl methacrylate, vinyl acetate, acrylonitrile, metering system Sour hydroxypropyl acrylate, acrylic acid 2- hydroxyl ethyl ester, methyl methacrylate, butyl methacrylate, methacryloxypropyl three (three Methyl silicane oxygroup) silane, the siloxanes acrylate or methacrylate and their mixture that replace.
19. silicone hydrogels according to any one of the preceding claims, the silicone hydrogels also include at least A kind of additional hydrophilic monomer.
20. silicone hydrogels according to any one of the preceding claims, wherein described (methyl) acrylic acid hydroxy alkyl Ester monomer is selected from (methyl) acrylic acid 2- hydroxyl ethyl ester, (methyl) acrylic acid 3- hydroxypropyl acrylate, (methyl) acrylic acid 2- hydroxypropyl acrylate, (first Base) bis- hydroxypropyl acrylate of acrylic acid 2,3-, (methyl) acrylic acid 2- hydroxy butyl ester, (methyl) acrylic acid 3- hydroxy butyl ester, 1- hydroxypropyl -2- (methyl) acrylate, (methyl) acrylic acid 2- hydroxy-2-methyl propyl ester, (methyl) acrylic acid 3- hydroxyl -2,2- dimethyl propylene Ester, (methyl) acrylic acid 4- hydroxy butyl ester, (methyl) glycerol acrylate, polyethylene glycol monomethacrylate and they Mixture.
21. silicone hydrogels described in any one of -19 according to claim 1, wherein described (methyl) acrylic acid hydroxy alkyl Ester monomer is selected from 2-Hydroxyethyl methacrylate, glyceral methacrylate, methacrylic acid 2- hydroxypropyl acrylate, hydroxyethyl methacrylate Butyl ester, methacrylic acid 3- hydroxyl -2,2- dimethyl propyl ester and their mixture or 2-Hydroxyethyl methacrylate, first Base acrylic acid 3- hydroxyl -2,2- dimethyl propyl ester, methacrylate or glyceral methacrylate and theirs is mixed Close object.
22. silicone hydrogels according to claim 19, wherein the additional hydrophilic monomer is selected from ethylene glycol ethyl ethers Alkene ether (EGVE), two (ethylene glycol) vinyl ethers (DEGVE), n-vinyl pyrrolidone (NVP), 1- methyl -3- methylene - 2-Pyrrolidone, 1- methyl -5- methylene -2-Pyrrolidone, 5- methyl -3- methylene -2-Pyrrolidone；1- ethyl -5- is sub- N-methyl-2-2-pyrrolidone N, N- methyl -3- methylene -2-Pyrrolidone, 5- ethyl -3- methylene -2-Pyrrolidone, 1- positive third Base -3- methylene -2-Pyrrolidone, 1- n-propyl -5- methylene -2-Pyrrolidone, 1- isopropyl -3- methylene -2- pyrroles Alkanone, 1- isopropyl -5- methylene -2-Pyrrolidone, N- vinyl-N-methylacetaniide (VMA), N- vinyl-N- ethyl Acetamide, N- vinyl-N-ethyl formamide, N- vinyl formamide, N- vinyl acetamide, N- vinyl isopropyl acyl Amine, allyl alcohol, N- caprolactam, carbamic acid N-2- hydroxyethyl vinyl base ester, N- carboxy-- alanine-N- ethylene Base ester；N- carboxyl vinyl-Beta-alanine (VINAL), N- carboxyl vinyl-α-alanine and their mixture.
23. silicone hydrogels according to claim 19, wherein the additional hydrophilic monomer is selected from N, N- diformazan Base acrylamide, n-vinyl pyrrolidone, N- vinyl-N-methylacetaniide, N- vinyl acetamide and 1- methyl- 5- methylene -2-Pyrrolidone.
24. silicone hydrogels according to claim 19, wherein the additional hydrophilic monomer includes N- vinyl Pyrrolidones, N, N- dimethylacrylamide and their mixture.
25. silicone hydrogels according to any one of the preceding claims, wherein first monofunctional hydroxyl replaces Poly- (two replace siloxanes) and second hydroxyl poly- (two replace siloxanes) that replaces with offer between 0.1 to 1.3 First monofunctional hydroxyl poly- (two replace siloxanes) that replace and second hydroxyl replace poly- (two replace silicon oxygen Alkane) the concentration of weight ratio be present in the reactive monomer mixture.
26. silicone hydrogels according to any one of the preceding claims, wherein first monofunctional hydroxyl replaces Poly- (two replace siloxanes) there is structure shown in Formula IV -1
Wherein
Z is selected from O, N, S or NCH2CH2O, when Z is O or S, R2It is not present；
R1It independently is H or methyl；
R2Straight chain for H or containing one to eight carbon atom, branch or cyclic alkyl radical, any one of them can be further by extremely A few hydroxyl group replaces, and it is optionally replaced by amide, ether and their combination；
R3And R4It independently is the straight chain containing one to eight carbon atom, branch or cyclic alkyl radical, any one of them can be into One step is replaced by least one hydroxyl group, amide, ether and their combination；R3And R4It can be independently selected from methyl, ethyl Or phenyl, or can be methyl；
N is 4-8, and
R5C selected from linear chain or branched chain1To C8Alkyl group, optionally by one or more hydroxyls, amide, ether and it Combination replace；Or R5For methyl or the C of linear chain or branched chain4Alkyl, any one of them are optionally optionally substituted by a hydroxyl group.
27. according to claim 1 or silicone hydrogels described in 26, wherein poly- (the dialkyl group silicon that second hydroxyl replaces Oxygen alkane) include Formula IV -2 compound
Wherein Z is selected from O, N, S or NCH2CH2O, when Z is O or S, R2It is not present；
R1It independently is H or methyl；
R2Straight chain for H or containing one to eight carbon atom, branch or cyclic alkyl radical, any one of them can be further by extremely A few hydroxyl group replaces, and it is optionally replaced by amide, ether and their combination；
R3And R4It independently is the straight chain containing one to eight carbon atom, branch or cyclic alkyl radical, any one of them can be into One step is replaced by least one hydroxyl group, and it is optionally replaced by amide, ether and their combination；R3And R4It can It independently selected from methyl, ethyl or phenyl, or can be methyl；
N is the number of siloxane unit and is 10 to 200；And
R5C selected from linear chain or branched chain1To C8Alkyl group, optionally by one or more hydroxyls, amide, ether and it Combination replace.
28. silicone hydrogels according to any one of the preceding claims, wherein first monofunctional hydroxyl replaces Poly- (dialkylsiloxane) and second hydroxyl replace poly- (dimethyl siloxane) total weight % between about 40 weights % and about 70 weight % or about 45 weight % is measured between about 70 weight %.
29. silicone hydrogels according to any one of the preceding claims, the silicone hydrogels also include to be selected from At least one below it is additional contain organosilicon composition: not hydroxyl contain organic silicon monomer, macromonomer, crosslinking agent.
30. silicone hydrogels according to claim 27, wherein poly- (two substitutions that first monofunctional hydroxyl replaces Siloxanes) in n=4-8, and the n=10-20 in second hydroxyl poly- (two replace siloxanes) that replace.
31. silicone hydrogels according to any one of the preceding claims, wherein first monofunctional hydroxyl replaces Poly- (dialkylsiloxane) and the weight ratio of poly- (dimethyl siloxane) that replaces of second hydroxyl between 0.1 and 1 or about Between 0.4 and 1.
32. silicone hydrogels according to claim 2 the, wherein poly- (dialkyl group that first monofunctional hydroxyl replaces Siloxanes) in siloxane repeat unit average be 4, and second hydroxyl replace poly- (dimethyl siloxane) in silicon The average of oxygen alkane repetitive unit is between 10 and 20.
33. silicone hydrogels described in any one of 9 or 22-24 according to claim 1, wherein additional hydrophilic monomer Total weight % is between about 5 weight % and about 30 weight % or about 8 weight % between about 25 weight %.
34. according to claim 1 to silicone hydrogels described in any one of 33, the silicone hydrogels also include to be selected from It is below at least one crosslinking agent: bifunctional crosslinking agent, trifunctional crosslinking agent, tetrafunctional crosslinking agent, polyfunctional crosslinking agent and Their mixture.
35. silicone hydrogels according to claim 27, wherein poly- (two substitutions that second monofunctional hydroxyl replaces Siloxanes) it is selected from poly- (two replace siloxanes) that the hydroxyl of Formula IV -2 replaces, wherein n is 10 to 20；The bifunctional hydroxy of Formula XI Poly- (two replace siloxanes) replaced；And their mixture
Wherein
R1It independently is hydrogen atom or methyl group；
R15And R16It independently is the straight chain containing one to eight carbon atom, branch or cyclic alkyl radical, any one of them can be into One step is replaced by least one hydroxyl group, acylamino-, ether, amino, carboxyl, carbonyl group and their combination；Or solely It is on the spot methyl or ethyl；And
N is 10 to 200；10 to 100；10 to 50；10 to 20.
36. silicone hydrogels according to claim 1, wherein poly- (the two substitution silicon oxygen that the monofunctional hydroxyl replaces Alkane) it is selected from poly- (dimethyl siloxane) that the monofunctional hydroxyl of Formula VII a-IXb replaces
Wherein R1For methyl or H；N is between 4 and 30,4-8 or 10-20；
R2Straight chain independently selected from H or containing one to eight carbon atom, branch or cyclic alkyl radical, any one of them can be into One step is replaced by least one hydroxyl group, and it is optionally replaced by amide, ether and their combination；
n1And n2Independently between 4 to 100；4 to 50；Or between 4 to 25；
n3For 1-50,1-20 or 1-10；
R5C selected from linear chain or branched chain1To C8Alkyl group, optionally by one or more hydroxyls, amide, ether, polyhydroxy Group replaces, and the polyhydroxy group, which is selected from, has formula CfHg(OH)hLinear chain or branched chain C1To C8Group, wherein f=1-8 and G+h=2f+1, and there is formula CfHg(OH)hCyclic annular C1To C8Group, wherein f=1-8 and g+h=2f-1 and they Combination；Or R5It can be selected from the C that methyl, butyl or hydroxyl replace2-C5Alkyl, including ethoxy, hydroxypropyl, hydroxyl butyl, hydroxyl penta Base and 2,3- dihydroxypropyl；
For the first hydroxyl organosilicon composition, a 4-8, and for the second hydroxyl organosilicon composition, a is situated between Between 4-100.
37. silicone hydrogels according to any one of the preceding claims, wherein described other group be selected from diluent, Ultraviolet absorber compounds, medicament, Antimicrobe compound, medical compounds, nutritional supplementation compound, photochromic chemical combination Object, reactive toner, pigment, copolymerizable dyestuff, non-polymeric dyestuff, release agent, copolymer and their combination.
38. the silicone hydrogels according to claim 37, wherein the ultraviolet absorber compounds are selected from reactivity 2- (2 '-hydroxy phenyl) benzotriazole, 2- dihydroxy benaophenonel, 2- hydroxyphenyltriazinuv, oxanilide, cyanoacrylate, water Poplar hydrochlorate, 4-HBA ester and their mixture.
39. the silicone hydrogels according to claim 37, wherein the ultraviolet absorber compounds are selected from 2- (2 '-hydroxyls Base -5- methaciylyloxyethylphenyl) -2H- benzotriazole, the 5- second of 2- (2,4- dihydroxy phenyl) -2H- benzotriazole The 4- acrylate or 4- methyl of alkenyl and 5- isopropenyl derivative and 2- (2,4- dihydroxy phenyl) -2H- benzotriazole Acrylate or 2- (2,4- dihydroxy phenyl) -1,3-2H- dibenzo triazole and their mixture.
40. silicone hydrogels according to any one of the preceding claims, wherein the silicone hydrogels have extremely Few about 80 Barres or about 80 Barres to about 200 Barres, about 90 Barres to about 180 Barres, about 100 Barres are saturating to about 160 Barres Oxygen (Dk).
41. silicone hydrogels according to any one of the preceding claims, the silicone hydrogels also include at least A kind of charge-carrying monomers, the charge-carrying monomers include at least one ionic portions selected from the following: anion, cation, both sexes from Son, glycine betaine and their mixture.
42. a kind of haptic lens, the haptic lens includes organosilicon water-setting according to any one of the preceding claims Glue.
43. haptic lens according to claim 42, wherein lysozyme absorptivity is at least 50 μ g, at least 100 μ g/ mirrors Piece, at least 200 μ g/ eyeglasses, at least 500 μ g/ eyeglasses, at least 700 μ g/ eyeglasses or at least 800 μ g/ eyeglasses；50-1500 μ g/ mirror Piece, 100-1500 μ g/ eyeglass or 200-1500 μ g/ eyeglass.
44. haptic lens according to claim 42, wherein lipid absorptivity is less than 15 μ g or less than 10 μ g/ eyeglasses.
45. wherein dynamic contact angle is less than about 95 ° according to haptic lens described in claim 42-44.
46. a kind of silicone hydrogels formed by reactive monomer mixture, the reactive monomer mixture includes:
A. at least one (methyl) acrylic acid hydroxy alkyl ester；
B. hydroxyl organosilicon composition, the hydroxyl organosilicon composition include the mixture of following item:
The straight chain that first hydroxyl of Formula IV replaces is poly- (dialkylsiloxane),
Wherein
Z is selected from O, N, S or NCH2CH2O, when Z is O or S, R2It is not present；
R1It independently is H or methyl；
R2Straight chain for H or containing one to eight carbon atom, branch or cyclic alkyl radical, any one of them can be further by extremely A few hydroxyl group replaces, and it is optionally replaced by amide, ether and their combination；
R3And R4It independently is the straight chain containing one to eight carbon atom, branch or cyclic alkyl radical, any one of them can be into One step is replaced by least one hydroxyl group, amide, ether and their combination；R3And R4It can be independently selected from methyl, ethyl Or phenyl, or can be methyl；
For poly- (two replace siloxanes) that first monofunctional hydroxyl replaces, n 4-8；And
The straight chain that second hydroxyl replaces is poly- (dialkylsiloxane), and the straight chain that second hydroxyl replaces is poly- (dialkylsiloxane) It is selected from:
The straight chain that the monofunctional hydroxyl of Formulas I replaces is poly- (dialkylsiloxane), and wherein n is 10 to 20, and R13Selected from optionally The C of the linear chain or branched chain replaced by one or more hydroxyls, amide, ether and their combination1To C8Alkyl group；And
The multifunctional hydroxyl of Formula XI with 10 to 500 or 10 to 200 or 10 to 100 siloxane repeat units replaces Straight chain it is poly- (dialkylsiloxane),
Wherein R1It independently is hydrogen atom or methyl group；
R15And R16It independently is the straight chain containing one to eight carbon atom, branch or cyclic alkyl radical, any one of them can be into One step is replaced by least one hydroxyl group, acylamino-, ether, amino, carboxyl, carbonyl group and their combination；Or solely It is on the spot methyl or ethyl；And
N is 10 to 200；10 to 100；10 to 50；10 to 20；
Poly- (the dioxane of straight chain that the straight chain poly- (dialkylsiloxane) and first hydroxyl that wherein second hydroxyl replaces replace Radical siloxane) ratio in the range of 0.1 to 1.3 or 0.4 to 1；
Total weight based on the reactive monomer mixture is greater than at least one polyamide of 15 weight %, the polyamide Selected from PVP, PVMA, PDMA, PNVA, polyacrylamide and their copolymer and mixture；And
Optionally, methacrylic acid.
47. silicone hydrogels according to claim 46, the silicone hydrogels also include at least one additional Hydrophilic monomer, the hydrophilic monomer are selected from N- vinylamide, N- vinyl acid imide, N- vinyl lactam, hydrophilic Property (methyl) acrylate, (methyl) acrylamide, hydrophily styrene, vinyl ethers, O- vinylcarbonates, O- vinyl Carbamate, N- vinyl urea, other hydrophilic ethylene based compounds and their mixture.
48. a kind of prepare according to claim 1 to the method for silicone hydrogels described in any one of 41 or 46-47, described Method includes:
Reactive monomer mixture is prepared, the reactive monomer mixture includes hydroxyalkyl (methyl) acrylamide monomer；The One and the second hydroxyl organosilicon composition；Polyamide；And any optional other component, wherein being based on the reactive monomer The total weight of mixture, the polyamide are present in the reactive monomer mixture with the amount greater than 15 weight %；With And
Solidify the reactive monomer mixture, to form silicone hydrogels.
49. a kind of silicone hydrogels formed by reactive monomer mixture, the reactive monomer mixture includes:
A. at least one polyamide between 15 weight % and about 40 weight %；
B. at least one hydroxyl siloxanyl monomers；
C. poly- (two replace siloxanes) that at least one hydroxyl replaces, poly- (two replace siloxanes) that the hydroxyl replaces, is selected from tool There is poly- (two replace siloxanes) of 4 to 8 siloxane repeat units, there are 10 to 200 or 10 to 100 siloxanes repetition lists Poly- (two replace siloxanes) and there are 10 to 200 or 10 to 100 siloxanes repetitions that the monofunctional hydroxyl of member replaces Poly- (two replace siloxanes) and their mixture that the multifunctional hydroxyl of unit replaces；
D. at least one hydrophilic monomer.
50. a kind of haptic lens, the haptic lens includes organosilicon water-setting according to any one of the preceding claims Glue.
51. haptic lens according to claim 50, wherein the lipid absorptivity is less than about 15 μ g/ eyeglasses.
52. haptic lens according to claim 50, wherein the lipid absorptivity is less than 10 μ g/ eyeglasses.
53. according to haptic lens described in claim 50-51, wherein the PQ1 absorptivity is less than about 20%.
54. according to haptic lens described in claim 50-51, wherein the dynamic contact angle is less than about 60 °.
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